Inorg. Chem.

1998, 37, 1749-1758 1749

16- and 18-Electron Ruthenium(II) Complexes of the Neutral, Potentially Tridentate

Triamine Ligand 2,6-[Bis(dimethylamino)methyl]pyridine (NN′N)

Rob A. T. M. Abbenhuis,† Ignacio del Rı́o,† Michel M. Bergshoef,† Jaap Boersma,†

Nora Veldman,‡ Anthony L. Spek,‡,⊥ and Gerard van Koten*,†
Debye Institute, Department of Metal-Mediated Synthesis, and Bijvoet Center for Biomolecular
Research, Laboratory of Crystal and Structural Chemistry, Utrecht University, Padualaan 8,
3584 CH Utrecht, The Netherlands
ReceiVed August 20, 1997

The potentially tridentate coordinating ligands NN′N (2,6-bis[(dimethylamino)methyl]pyridine) and PNP (2,6-
bis[(diphenylphosphino)methyl]pyridine) react with [RuCl2(PPh3)3] to give [mer,trans-RuCl2(NN′N)(PPh3)] (1)
and [mer,trans-RuCl2(PNP)(PPh3)] (2), respectively. Complex 1 functions as a starting material for a variety of
Ru[NN′N] complexes. It reacts with either 1 or 2 equiv of AgOTf (OTf- ) SO3CF3-) to yield monocationic
[RuCl(NN′N)(PPh3)]OTf (3) and [RuOTf(NN′N)(PPh3)]OTf (4), respectively. The molecular structure of 4 shows
a pentacoordinated ruthenium(II) center with a square-pyramidal environment. The reaction of 1 with either 1 or
2 equiv of AgOTf in the presence of MeCN results in the formation of the six-coordinate mono- or dicationic
complexes [mer-RuCl(MeCN)(NN′N)(PPh3)]X (6a) (X ) OTf-) and [mer,trans-Ru(MeCN)2(NN′N)(PPh3)](OTf)2
(7), respectively. At 55 °C in acetonitrile, 1 converts quantitatively into 6b (X ) Cl-) which is isostructural with
6a. Reaction of polymeric [RuCl2(nbd)]n (nbd ) 2,5-norbornadiene) with NN′N under a nitrogen atmosphere
leads to the formation of neutral, dinitrogen-bridged dimeric [(µ-N2)(mer,trans-RuCl2{NN′N})2] (8). The dinitrogen
ligand is readily replaced when 8 is treated with CO, giving the neutral complex [mer,trans-RuCl2(CO)(NN′N)]
(9). The 16-electron complex 3 reacts with CO giving [mer,cis-RuCl(CO)2(NN′N)]OTf (10), involving the
formation of [RuCl(CO)(NN′N)(PPh3)]OTf (11), followed by substitution of PPh3 by a second CO molecule.
This stepwise mechanism was confirmed by the isolation of 11. The 16-electron complex 4 reacts with CO
under the formation of monocationic [mer-RuOTf(CO)(NN′N)(PPh3)]OTf (12) and a number of unidentified
complexes. In the presence of ethyl alcohol, 4 reacts with CO to give monocationic [mer-RuOTf(CO)(NN′N)-
(HOEt)]OTf (13). The X-ray crystal structures of 1, 4, 6a, 8, 11, and 13 are reported in abbreviated form.

Introduction which a central pyridine ring contains bis-ortho (a)chiral

Although a wide range of (chiral) bidentate ligands has been phosphine substituents.7 We are currently investigating the use
used in (asymmetric) catalysis,1-3 application of terdentate, of monoanionic, terdentate ligand systems [C6H3(CH2NMe2)2-
especially neutral C2 symmetrical, ligands in homogeneous 2,6]- ([NCN]-) or [C6H3(CH2PPh2)2-2,6]- ([PCP]-) which
catalysis3-4 has received much less attention. Recently, a differ from neutral tridentate ligands NN′N and PNP by the
number of such terdentate ligands, bearing three sp2-hybridized fact that NCN and PCP are bonded to the (transition) metal by
nitrogen donor atoms, have been reported, e.g. bis(oxazolinyl)- a metal-carbon σ bond (see Figure 1).8,9
pyridines5 and bis(pyrazolyl)pyridines (“pybox”).6 Moreover, Ruthenium(II) complexes containing the [NCN]- and [PCP]-
a number of related C2 symmetrical, neutral, mixed phosphorus- ligand systems have proven to be very active catalysts in base
nitrogen tridentate ligands of type PNP have been reported, in co-catalyzed hydrogen-transfer reactions of ketones and imines
with 2-propanol.10,11 In these reactions, turnover numbers up
* To whom correspondence should be addressed. E-mail address: to 25 000 were observed.12 Recently, we have also developed
[email protected]. Fax: +31 30 252 3615. C2 symmetric chiral analogs of the [NCN]- ligand by introduc-
† Debye Institute.
‡ Bijvoet Center for Biomolecular Research. ing chirality at the benzylic carbon atom positions.13 In order
⊥ To whom correspondence on crystallographic studies should be
to study the effect of the replacement of a metal-carbon σ bond
addressed. E-mail address: [email protected]. in NCN and PCP metal complexes by a metal-nitrogen
(1) Togni, A.; Venanzi, L. M. Angew. Chem., Int. Ed. Engl. 1994, 33,
497-526.
(2) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley: New (7) (a) Jiang, Q.; Van Plew, D.; Murtuza, S.; Zhang, X. Tetrahedron Lett.
York, 1994. 1996, 37, 797. (b) Sablong, R.; Newton, C.; Dierkes, P.; Osborn, J.
(3) Taqui Khan, M. M.; Martell, A. E. Homogeneous Catalysis by Metal A. Tetrahedron Lett. 1996, 37, 4933. (c) Sablong, R.; Osborn, J. A.
Complexes; Academic Press: New York, 1974; Vols. I and II. Tetrahedron Lett. 1996, 37, 4937. (d) Barloy, L.; Ku, S. Y.; Osborn,
(4) (a) For a review on multidentate phosphines, see: Mayer, H. A.; Kaska, J. A.; De Cian, A.; Fischer, J. Polyhedron 1997, 16, 291.
W. C. Chem. ReV. 1994, 94, 139. (b) For a review on the NCN- ligand, (8) van Koten, G. Pure Appl. Chem. 1989, 61, 1681-1694.
see: Rietveld, M.; Grove, D. M.; van Koten, G. New J. Chem. 1997, (9) Karlen, T.; van Koten, G. Manuscript in preparation.
21, 751-771. (10) Sutter, J.-P.; Steenwinkel, P.; Karlen, T.; Grove, D. M.; Veldman,
(5) (a) Nishiyama, H.; Sakaguki, H.; Nakamura, T.; Horihata, M.; Kondo, N.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics
M.; Itoh, K. Organometallics 1989, 9, 846. (b) Nishiyama, H.; Kondo, 1996, 15, 941-948.
M.; Nakamura, T.; Hoh, K. Organometallics 1991, 10, 500. (11) Karlen, T.; Dani, P.; Grove, D. M.; Steenwinkel, P.; van Koten, G.
(6) Christenson, D. L.; Toker, C. J.; Tolman, W. B. Organometallics 1995, Organometallics 1996, 15, 5687-5694.
14, 2148. (12) Karlen, T.; Grove, D. M.; van Koten, G. Manuscript in preparation.

S0020-1669(97)01061-6 CCC: $15.00 © 1998 American Chemical Society

Published on Web 03/31/1998
1750 Inorganic Chemistry, Vol. 37, No. 8, 1998 Abbenhuis et al.

solution of PNP (1.86 g, 3.92 mmol) in CH2Cl2 (10 mL). After the
mixture was stirred for 30 min, the solvent was removed in Vacuo and
the residue extracted with Et2O (20 mL, 2×), leaving the pure product
as a yellow solid (3.35 g, 94%). No decomposition at T < 200 °C. 1H
NMR (CDCl3, ppm): δ 7.53 (t, 1H, p-H py), 7.45-7.20 (m, 22H, ar-
H), 7.15-7.00 (m, 10H, ar-H), 6.90-6.85 (m, 5H, m-H py and ar-H),
Figure 1. Ligands used and their abbreviations. 4.55 (t, |2JHP + 4JHP| ) 9.4 Hz, 4H, CH2). 13C NMR (CDCl3, ppm):
δ 162.36 (o-C pyr), 137.75 (d, 1JPC ) 39.9 Hz, ipso-C PPh2), 136.55
coordinate bond, we applied the neutral pyridine analogue (p-C py), 134.82 (d, 3JPC ) 9.3 Hz, m-C PPh3), 133.78 (t, JPC ) 9.6
[C5H3N(CH2NMe2)2-2,6] (NN′N) to ruthenium coordination Hz, m-C PPh2), 133.12 (t, JPC ) 38.0 Hz, ipso-C PPh3), 129.03 (p-C
chemistry.14 Like the [NCN]- ligand, neutral NN′N contains PPh2), 128.36 (p-C PPh3), 127.54 (t, JPC ) 8.4 Hz, o-C PPh2), 127.74
two flexible ortho-CH2NMe2 substituents, each carrying a (d, JPC ) 8.9 Hz, o-C PPh3), 120.47 (m-C py), 46.98 (t, JPC ) 4.1 Hz,
tertiary amine donor atom. Furthermore, the NN′N ligand has CH2). 31P NMR (CDCl3, ppm): δ 41.83 (t, 1P, JPP ) 29 Hz, PPh3),
some similarity with the well-known 2,2′,6:2′′-terpyridine (terpy) 35.41 (d, 2P, JPP ) 29 Hz, PPh2). UV/vis, λmax (): 327 (5136), 398
but differs with respect to the nature of two of the N-donor (2351). Anal. Calcd for C49H42Cl2N3P3Ru: C, 64.69; H, 4.65; N, 1.54.
atoms. Where terpyridine contains three sp2-hybridized nitrogen Found: C, 64.55; H, 4.40; N, 1.47.
donor atoms, the NN′N ligand is based on a combination of Synthesis of [RuCl(NN′N)(PPh3)]OTf (3). To a solution of 1 (0.65
one sp2- and two sp3-hybridized donor atoms. Moreover, the g, 1.04 mmol) in CH2Cl2 (50 mmol) was added solid AgOTf (0.27 g,
use of terpyridine is restricted to 18-electron complexes. In 1.04 mmol). After it was stirred for 45 min, the reaction mixture had
changed color from brown to purple, and a newly formed flaky white
this paper, we report on the synthesis, characterization, and
precipitate was filtered off. The volume of the remaining solution was
reactivity of 16- and 18-electron ruthenium(II) complexes of reduced in Vacuo to 3 mL. Pentane (20 mL) was added upon which
the NN′N ligand [C5H3N(CH2NMe2)2-2,6]. the product precipitated. After filtration and subsequent drying in
Vacuo, the pure product was isolated as a purple solid (0.61 g, 92%).
Experimental Section No decomposition at T < 200 °C. 1H NMR (acetone-d6, ppm): δ
Syntheses were performed in a dry, oxygen-free nitrogen atmosphere 7.90-7.80 (m, 6H, m-H PPh3), 7.48-7.30 (m, 12H, ar-H and py-H),
using standard Schlenk techniques. Et2O (predried on CaH2) and 4.05 (d, 2JHAHB ) 16.2 Hz, CHAHB), 3.51 (d, 2JHAHB ) 16.2 Hz, CHAHB),
pentane were carefully dried and distilled from sodium benzophenone 2.68 (s, 6H, N(Me)(Me)), 2.32 (s, 6H, N(Me)(Me)). 13C NMR (acetone-
ketyl prior to use. 1H, 13C, and, 31P NMR spectra were recorded on d6, ppm): δ 162.7 (o-C py), 137.3 (p-C py), 134.4 (d, 3JPC ) 9.9 Hz,
200 and 300 MHz spectrometers at 298 K. 1H and 13C chemical shifts m-C PPh3), 134.3 (d, 1JPC ) 51.9 Hz, ipso-C PPh3), 131.2 (d, 4JPC )
are referenced to Me4Si, and 31P NMR data to 85% H3PO4, respectively. 2.7 Hz, p-C PPh3), 129.2 (d, 2JPC ) 10.5 Hz, o-C PPh3), 122.6 (m-C
19F shifts were referenced to CFCl . IR measurements were made on py), 73.7 (CH2), 52.8 (N(Me)(Me)), 47.6 (N(Me)(Me)). 31P NMR
3
a FT-IR spectrophotometer set to a resolution of 2 cm-1. Raman (acetone-d6, ppm): δ 86.6 (PPh3). UV/vis, λmax (): 365 (11 144), 530
measurements were performed on a spectrophotometer equipped with (3500). Anal. Calcd for C30H34ClF3N3O3PRuS: C, 48.61; H, 4.62;
a Nd:YAG laser using a laser power of 10 mW set to a resolution of N, 5.67. Found: C, 48.25; H, 4.44, N, 5.66.
2 cm-1 in combination with an InGaAs detector. FAS-MS spectra were Synthesis of [RuOTf(NN′N)(PPh3)]OTf (4). To a solution of 1 (1
recorded using Cs as a bombardment gas and NBA as a matrix. g, 1.6 mmol) in CH2Cl2 (50 mL) was added AgOTf (0.85 g, 3.2 mmol).
Elemental analyses were carried out by Dornis und Kölbe, Microana- After the suspension was stirred for 30 min, a newly formed flaky white
lytisches Laboratorium (Mülheim a.d. Ruhr, Germany). RuCl2(PPh3)3,15 precipitate was filtered off, and from the remaining purple solution
RuCl2(PMe3)4,16 [RuCl2(norbornadiene)]n,17 2,6-bis[(dimethylamino)- the solvent was removed in Vacuo, leaving a purple solid as the pure
methyl]pyridine (NN′N),14 and 2,6-bis[(diphenylphosphino)methyl]- product (1.27 g, 93%). No decomposition at T < 200 °C. 1H NMR
pyridine (PNP),18 were prepared according to literature procedures. Full (CDCl3, ppm): δ 7.75 (t, 1H, p-H py), 7.49-7.40 (m, 9H, ar-H), 7.32-
1H, 13C, and 31P NMR data of the ligands are added as Supporting
7.25 (m, 8H, ar-H), 3.95 (d, 2JHAHB ) 16 Hz, CHAHB), 3.21 (d, 2JHAHB
Information. ) 16 Hz, CHAHB), 2.71 (s, 6H, N(Me)(Me)), 2.31 (s, 6H, (NMe)(Me)).
Synthesis of [mer,trans-RuCl2(NN′N)(PPh3)] (1). To a solution 13C NMR (CDCl , ppm): δ 162.6 (o-C py), 137.8 (p-C py), 133.4 (d,
3
of RuCl2(PPh3)3 (0.67 g, 0.70 mmol) in CH2Cl2 (50 mL) was added a 3J
PC ) 9.6 Hz, m-C PPh3), 131.6 (d, JPC ) 46.1 Hz, ipso-C PPh3),
1
solution of NN′N (0.14 g, 0.70 mmol) in CH2Cl2 (5 mL) over 1 min. 131.3 (p-C PPh3), 128.9 ( JPC ) 10.6 Hz, o-C PPh3), 122.6 (m-C py),
2
After the mixture was stirred for 30 min, the solvent was removed in 118.50 (q, 1JCF ) 310 Hz, SO3CF3), 72.1 (CH2), 52.6 (N(Me)(Me)),
Vacuo. The remaining brown oil was extracted with Et2O (10 mL, 45.7 (N(Me)(Me)). 31P NMR (CDCl3, ppm): δ 74.5 (PPh3). UV/vis,
2×) leaving a yellow brown solid as the pure product (0.42 g, 96%). λmax (): 342 (5532), 508 (1691). Anal. Calcd for C31H34F6N3O6-
No decomposition at T < 200 °C. 1H NMR (CDCl3, ppm): δ 8.15 (t, PRuS2: C, 43.56; H, 4.01; N, 4.92. Found: C, 43.42; H, 4.08; N,
6H, o-H PPh3), 7.65 (t, 1H, p-H py), 7.34-7.25 (m, 11H, m-H py, 4.86.
ar-H), 4.00 (s, 4H, CH2), 2.10 (s, 12H, NMe2). 13C NMR (CDCl3,
Synthesis of [mer-RuCl(MeCN)(NN′N)(PPh3)]OTf (6a). To a
ppm): δ 161.7 (o-C py), 138.9 (d, 1JPC ) 31.7 Hz, ipso-C PPh), 135.0
solution of 1 (0.16 g, 0.25 mmol) in CH2Cl2 (30 mL)/MeCN (5 mL)
(p-C py), 134.4 (d, 3JPC ) 9.2 Hz, m-C PPh3), 128.3 (p-C PPh), 127.5
(d, 2JPC ) 8.3 Hz, o-C PPh3), 119.3 (m-C py). 31P NMR (CDCl3, was added AgOTf (0.07 g, 0.27 mmol). After the reaction mixture
ppm): δ 37.0 (PPh3). UV/vis, λmax (): 390 (4949). Anal. Calcd for was stirred for 30 min, a newly formed flaky white precipitate was
C29H34Cl2N3PRu: C, 55.50; H, 5.46; N, 6.70. Found: C, 55.38; H, filtered off. After the solvent was removed in Vacuo, the crude product
5.37; N, 6.66. was extracted with Et2O (10 mL, 2×), leaving the pure product as a
Synthesis of [mer,trans-RuCl2(PNP)(PPh3)] (2).7d To a solution light brown solid (0.18 g, 90%). No decomposition at T < 200 °C. 1H
of RuCl2(PPh3)3 (3.76 g, 3.92 mmol) in CH2Cl2 (50 mL) was added a NMR (CDCl3, ppm): δ 8.13 (t, 6H, o-H PPh3), 7.87 (t, 1H, p-H py),
7.47 (d, 2H, m-H py), 7.44-7.36 (m, 9H, ar-H), 4.30 (d, 2H, 2JHAHB )
(13) Donkervoort, J. G.; Jastrzebski, J. T. B. H.; van Koten, G. J.
15 Hz, CHAHB), 3.89 (d, 2H, 2JHAHB ) 15 Hz, CHAHB), 2.37 (s, 6H,
Organomet. Chem., in press. N(Me)(Me)), 2.11 (s, 6H, N(Me)(Me)), 1.91 (s, 3H, MeCN). 13C NMR
(14) Markies, B. M.; Wijkens, P.; Kooijman, H.; Veldman, N.; Spek, A. (CDCl3, ppm): δ 159.6 (o-C py), 137.8 (p-C py), 136.1 (d, 1JPC )
L.; Boersma, J.; van Koten, G. Organometallics 1994, 13, 3244- 35.5 Hz, ipso-C PPh3), 133.0 (d, 3JPC ) 9.8 Hz, m-C PPh3), 129.4 (p-C
3258. PPh3), 128.6 (d, 2JPC ) 8.8 Hz, o-C PPh3), 127.3 (MeCN), 121.0 (m-C
(15) Holm, R. Inorg. Synth. 1970, 12, 238. py), 73.6 (CH2), 55.7 (N(Me)(Me)), 55.1 (N(Me)(Me)), 4.1 (MeCN).
(16) Singer, H. E.; Hademer, E.; Oechmichen, U.; Dixneuf, P. J. Orga- 31P NMR (CDCl , ppm): δ 32.8 (PPh ). UV/vis, λ
nomet. Chem. 1979, 178, C13. 3 3 max (): 350 (4663).
(17) Abel, E. W.; Bennett, M. A.; Wilkinson, G. J. Chem. Soc. 1959, 3178. Anal. Calcd for C32H37ClF3N4O3PRuS: C, 49.13; H, 4.77; N, 7.16.
(18) Danlhoff, W. V.; Nelson, S. M. J. Chem. Soc. A 1971, 2184. Found: C, 48.96; H, 4.72; N, 7.06.
16- and 18-Electron Ru(II) Complexes of NN′N Inorganic Chemistry, Vol. 37, No. 8, 1998 1751

Synthesis of [mer-RuCl(MeCN)(NN′N)(PPh3)]Cl (6b). A suspen- distribution. Fractional crystallization by slow diffusion of pentane in
sion of 1 (0.31 g, 0.49 mmol) in acetonitrile (30 mL) was gently heated a CH2Cl2 solution of the crude product afforded almost pure product
to 55 °C for 5 min, upon which a clear brown solution was formed. as a light-yellow microcrystalline solid (0.2 g, 20%). No decomposition
After MeCN was evaporated, the crude product was dissolved in CHCl3 at T < 200 °C. 1H NMR (CD3CN, ppm): δ 7.96 (t, 1H, p-H py), 7.54
(25 mL). After pentane (50 mL) was added, the pure product was (d, 2H, m-H py), 4.36 (d, 2JHAHB ) 16.2 Hz, CHAHB), 4.13 (d, 2JHAHB
collected by centrifugation as a cream-colored solid (0.30 g, 91%). 1H ) 16.2 Hz, CHAHB), 2.84 (s, 6H, N(Me)(Me)), 2.66 (s, 6H, N(Me)-
NMR (CDCl3, ppm): δ 8.13 (t, 6H, o-H py), 7.84 (t, 1H, p-H py), (Me)). 13C NMR (CD3CN, ppm): δ 206.42, 200.98 (CO), 160.92 (o-C
7.53 (d, 2H, m-H py), 7.44-7.35 (m, 9H, ar-H py), 4.33 (d, 2H, 2JHAHB py), 139.61 (p-C py), 122.52 (m-C py), 74.24 (CH2), 58.36 (N(Me)-
) 15.5 Hz, CHAHB), 4.12 (d, 2H, 2JHAHB ) 15.5 Hz, CHAHB), 2.36 (s, (Me)), 54.27 (N(Me)(Me)). IR (KBr): νCO 1967, 1936 cm-1. Anal.
6H, N(Me)(Me)), 2.15 (s, 3H, MeCN), 2.12 (s, 6H, N(Me)(Me)). 13C Calcd for C14H19ClF3N3O5RuS: C, 31.43; H, 3.58; N, 7.86. Found:
NMR (CDCl3, ppm): δ 159.7 (o-C py), 137.6 (p-C py), 136.1 (d, 1JPC C, 26.40; H, 3.85; N, 6.63.
) 35.1 Hz, ipso-C PPh3), 133.0 (d, 3JPC ) 9.3 Hz, m-C PPh3), 129.3 Synthesis of [mer-RuCl(CO)(NN′N)(PPh3)]OTf (11). Through a
(p-C PPh3), 128.6 (d, 2JPC ) 8.8 Hz, o-C PPh3), 127.6 (MeCN), 121.0 solution of 3 (0.8 g, 1.15 mmol) in CH2CH2 (10 mL) was bubbled CO
(m-C py), 73.9 (CH2), 55.8 (N(Me)(Me)), 55.3 (N(Me)(Me)), 5.6 until the purple color of the solution had disappeared and the reaction
(MeCN). 31P NMR (CDCl3, ppm): δ 33.0 (PPh3). UV/vis, λmax (): mixture had turned light brown (2-3 min). Slow diffusion of pentane
350 (4609). Anal. Calcd for C31H37Cl2N4PRu‚3/2CH2Cl2: C, 49.04; into the reaction mixture gave the pure product as large pale yellow-
H, 5.07; N, 7.04. Found: C, 49.36; H, 5.10; N, 7.27. brown crystals which proved to contain 1 equiv of dichloromethane
Synthesis of [mer,trans-Ru(MeCN)2(NN′N)(PPh3)]OTf2 (7). To (0.82 g, 83%). 1H NMR (CD2Cl2, ppm): δ 8.22-8.10 (m, 6H, o-H
a solution of 1 (0.75 g, 1.2 mmol) in CH2Cl2 (30 mL)/MeCN (5 mL) PPh3), 8.03 (t, 1H, p-H py), 7.65 (d, 2H, m-H py), 7.51-7.48 (m, 9H,
was added AgOTf (0.61 g, 2.4 mmol). After the suspension was stirred ar-H), 4.63 (d, 2H, 2JHAHB ) 15.7 Hz, CHAHB), 3.97 (d, 2H, 2JHAHB )
for 30 min, the newly formed flaky white precipitate was filtered off. 15.7 Hz, CHAHB), 2.50 (s, 6H, N(Me)(Me)), 2.48 (s, 6H, N(Me)(Me)).
After the solvent was removed in Vacuo and the residue had been 13
C NMR (CD2Cl2, ppm): δ 200.52 (d, 2JPC ) 13.6 Hz, CO), 159.78
extracted with Et2O (10 mL, 2×), the pure product was obtained as a (o-C py), 142.13 (p-C py), 136.01 (d, 1JPC ) 41.4 Hz, ipso-C PPh3),
yellow solid (0.97 g, 86%). No decomposition at T < 200 °C. 1H 134.73 (d, 3JPC ) 8.9 Hz, m-C PPh3), 132.58 (d, 4JPC ) 1.9 Hz, p-C
NMR (DMSO-d6, ppm): δ 8.11 (t, 1H, p-H py), 7.77-7.71 (m, 8H, PPh3), 131.04 (d, 2JPC ) 9.4 Hz, o-C PPh3), 123.92 (m-C py), 76.66
ar-H), 7.55-7.46 (m, 9H, ar-H), 4.14 (s, 4H, CH2), 2.41 (s, 6H, MeCN), (CH2), 60.46 (N(Me)(Me)), 57.11 (N(Me)(Me)). 31P NMR (CD2Cl2,
2.20 (s, 12H, NMe2). 13C NMR (DMSO-d6, ppm): δ 161.4 (o-C py), ppm): δ 17.31 (PPh3). IR (KBr): νCO 1964 cm-1. UV/vis, λmax ():
141.8 (p-C py), 136.5 (d, 1JPC ) 37.9 Hz, ipso-C PPh3), 135.0 (d, 3JPC 238 (39 950). Anal. Calcd for C31H34ClF3N3O4PRuS‚CH2Cl2: C,
) 9.8 Hz, m-C PPh3), 132.5 (p-C PPh3), 132.3 (MeCN), 123.2 (q, 1JCF 45.00; H, 4.25; N, 4.92. Found: C, 44.64; H, 4.18; N, 4.87.
) 322 Hz, SO3CF3), 75.1 (CH2), 57.2 (NMe2), 6.73 (MeCN). 31P NMR [mer,cis-RuOTf(CO)(NN′N)(PPh3)]OTf (12). 1H NMR (CDCl3,
(DMSO-d6, ppm): δ 37.4 (PPh3). UV/vis, λmax (): 282 (5933). Anal. ppm): δ 7.95 (t, 1H, p-H py), 7.50 (d, 2H, m-H py), 7.45-7.05 (m,
Calcd for C35H40F6N5O6PRuS2: C, 44.87; H, 4.30; N, 7.47. Found: 15H, ar-H), 4.58 (d, 2H, 2JHAHB ) 16.5 Hz, CHAHB), 4.11 (d, 2H, 2JHAHB
C, 44.72; H, 4.31; N, 7.38. ) 16.5 Hz, CHAHB), 2.97 (s, 6H, N(Me)(Me)), 2.76 (s, 6H, N(Me)-
Synthesis of [(µ-N2)(mer,trans-RuCl2(NN′N))2] (8). To a suspen- (Me)). 31P NMR (CDCl3, ppm): δ 7.94 (PPh3). IR (KBr): νCO 1964
sion of [RuCl2(nbd)]n (1.28 g, 4.85 mmol) in C6H6 (100 mL) was added cm-1.
NN′N (1.02 g, 5.28 mmol) at room temperature, after which the reaction Synthesis of [mer-RuOTf(CO)(NN′N)(HOEt)]OTf (13). To a
mixture was refluxed for 24 h. Subsequently the solvent was removed solution of 4 (1.0 g, 1.17 mmol) in a mixture of CH2Cl2 (8 mL) and
in Vacuo. The resulting residue was extracted with CH2Cl2 (20 mL), EtOH (2 mL) was bubbled CO for 2 min, during which the color of
separated from insoluble starting material, and extracted with pentane the solution changed from purple to clear light yellow. Slow diffusion
(20 mL, 2×). After the solvent was removed in Vacuo, almost pure of pentane into the reaction mixture afforded the pure product as large
crude product was obtained in about 60% yield. Slow diffusion of yellow to orange block-shaped crystals (0.3 g, 38%). No NMR data
Et2O into a CH2Cl2 solution of this crude product resulted in the could be obtained due to instability and/or insolubility in different
formation of yellow-brown, block-shaped crystals (1.0 g, 30%). 1H deuterated solvents. IR (KBr): νCO 1968 cm-1. UV/vis, λmax (): 230
NMR (CDCl3, ppm): δ 7.60 (t, 1H, p-H py), 7.27 (d, 2H, m-H py), (7700), 264 (5287). Anal. Calcd for C16H25F6N3O8RuS2: C, 28.83;
4.15 (s, 4H, CH2), 2.80 (s, 12H, NMe2). 13C NMR (CDCl3, ppm): δ H, 3.78; N, 6.30. Found: C, 28.76; H, 3.86; N, 6.25.
162.5 (o-C py), 134.6 (p-C py), 119.5 (m-C py), 71.7 (CH2), 55.0 Substitutional Reactivity of [mer,trans-RuCl2(NN′N)(PPh3)] (1)
(NMe2). FAB-MS 760.0 (M+). Raman (cm-1): 2099 (NtN). UV/ toward PMe3. To a solution of 1 (0.45 g, 0.72 mmol) in CH2Cl2 (50
vis, λmax (): 426 (14 632). Anal. Calcd for C22H38Cl4N8Ru2: C, 34.84; mL) was added a solution of PMe3 (133 mg, 1.75 mmol) in MeOH
H, 5.05; N, 14.77. Found: C, 33.54; H, 4.80; N, 13.27 (incorrect, but (2.5 mL), which led to a slight color change from brown to reddish
C/H, C/N, and H/N ratios consistent with 8‚xRuCly). brown. 31P{1H} and 1H NMR of the resulting solution indicated that
Synthesis of [mer,trans-RuCl2(CO)(NN′N)] (9). Through a solution RuCl2(PMe3)4 (by comparison with an authentic sample16) had been
of 8 (100 mg, 0.132 mmol) in CH2Cl2 (20 mL) was bubbled CO for formed. 1H NMR (CDCl3, ppm): δ 1.50 (s, PMe3). 13C NMR (CDCl3,
90 min at room temperature, during which the color of the solution ppm): δ 17.42 (m, PMe3). 31P NMR (CDCl3, ppm): δ -5.95.
changed from green-yellow to light brown. After this, the solvent was
removed in Vacuo and the residue was extracted with pentane (10 mL), Crystal Structure Determinations
upon which the pure product remained as a green-brown solid (100
All crystals were sampled and mounted with the oil technique and
mg, 96%, based on 8). 1H NMR (CD2Cl2, ppm): δ 7.93 (t, 1H, p-H
cut to size when needed. X-ray data were collected at 150 K on an
py), 7.48 (d, 2H, m-H py), 4.22 (s, 4H, CH2), 2.68 (s, 12H, NMe2). 13C
Enraf-Nonius CAD4T on a rotating anode using graphite-monochro-
NMR (CD2Cl2, ppm): δ 185.4 (CO), 160.1 (o-C py), 139.0 (m-C py),
mated Mo KR radiation. Unit cell parameters were derived from the
121.0 (m-C py), 72.5 (CH2), 56.4 (NMe2). IR (KBr): νCO 1948 cm-1.
SET419 setting angles of 25 reflections. Unit cells were checked for
Anal. Calcd for C12H19Cl2N3ORu: C, 36.65; H, 4.87; N, 10.68.
higher symmetry with the programs LEPAGE20 and PLATON/
Found: C, 36.52; H, 4.85; N, 10.54.
MISSYM.21 All geometrical calculations and the ORTEP illustrations
Synthesis of [mer,cis-RuCl(CO)2(NN′N)]OTf (10). Through a
were done with PLATON22 (Table 1).
solution of 3 (1.64 g, 1.92 mmol) in CH2Cl2 (10 mL) was bubbled CO
[mer,trans-RuCl2(NN′N)(PPh3)] (1). A total of 23 464 reflections
for 4 min, upon which a distinct color change from deep purple to
(θmax ) 25°) were scanned and averaged into a unique set of 5795
clear yellow was observed. After the reaction mixture was stirred for
30 min under a CO atmosphere, pentane (40 mL) was added, upon
which a yellow solid precipitated. 1H NMR analysis confirmed that (19) (a) de Boer, J. L.; Duisenberg, A. J. M. Acta Crystallogr. 1984, A40,
C410. (b) Le Page, Y. J. Appl. Crystallogr. 1987, 20, 264-269.
this crude product consisted of about 80% of 10 along with 20% of (20) Spek, A. L. J. Appl. Crystallogr. 1988, 21, 578-579.
11. Further treatment of the crude product with CO in a CH2Cl2 (21) Spek, A. L. Am. Cryst. Assoc. 1997 (Abstract).
solution (10 mL) did not lead to significant improvement of product (22) Spek, A. L. Acta Crystallogr. 1990, A46, C34.
1752 Inorganic Chemistry, Vol. 37, No. 8, 1998 Abbenhuis et al.

Table 1. Experimental Data for the X-ray Diffraction Studies of 1, 4, 6a, 8, 11, and 13
1 4 6a 8 11 13
empirical formula C29H34Cl2N3PRu‚ C30H34F3N3O3PRuS‚ C31H37ClN4PRu‚ C22H38Cl4N8Ru2‚ C30H34ClN3OPRu‚ C15H25F3N3O5RuS‚
3/ CH Cl
2 2 2 CF3SO3‚CH2Cl2 CF3SO3‚2.75CHCl3 1/ C H O
2 4 10 CF3SO3‚5/4CH2Cl2 CF3SO3
fw 754.96 939.73 1110.51 795.61 875.35 666.58
color orange red yellow red yellowish yellowish
space group Fdd2 (No. 43) P1h (No. 2) P1h (No. 2) P21/c (No. 14) P212121 (No. 19) P21 (No. 4)
a (Å) 23.472(9) 9.3763(10) 12.4610(8) 14.8201(12) 12.335(1) 10.169(1)
b (Å) 59.277(13) 13.484(5) 17.460(2) 14.0198(12) 21.523(2) 10.313(1)
c (Å) 9.4320(10) 15.946(3) 22.737(2) 15.1417(11) 27.393(2) 12.214(1)
R (deg) - 84.23(2) 111.485(9) - - -
â (deg - 75.469(11) 91.413(6) 93.243(5) - 101.19(1)
γ (deg) - 78.13(2) 97.951(7) - - -
V (Å3) 13123(6) 1907.3(9) 4543.6(8) 3141.0(4) 7272(1) 1256.6(2)
λ (Mo KR) (Å) 0.710 73 0.710 73 0.710 73 0.710 73 0.710 73 0.710 73
Z 16 2 4 4 8 2
dcalc (g‚cm-3) 1.528 1.636 1.623 1.682 1.599 1.762
µ (Mo KR) (cm-1) 9.6 7.7 10.11 13.09 8.36 8.8
R1 [I > 2σ(I)]a 0.0738 0.0720 0.0529 0.0297 0.0589 0.0231
wR2 0.1799 0.1893 0.1436 0.0771 0.1263 0.0593
a R1 ) ∑(Fo - |Fc|)/∑Fo; wR2 ) [∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2.

reflections (5083 with I > σ(I)). The structure was solved by automated direct methods with SIR29 and refined on F2 with SHELXL96.28
Patterson methods (DIRDIF23) and refined on F2 with SHELXL93.24 Hydrogen atoms were taken into account at calculated positions. The
Hydrogen atoms were taken into account at calculated positions. racemic twin parameter for this model refined to 0.05(3).
[RuOTf(NN′N)(PPh3)]OTf (4). A total of 7294 reflections (θmax
) 25.4°) were scanned and averaged into a unique set of 6851 Results and Discussion
reflections (4903 with I > 2σ(I)). The structure was solved by
automated Patterson methods (DIRDIF23) and refined on F2 with The synthesis and reaction routes of the new EN′E-
SHELXL93.24 No satisfactory disorder model for the CH2Cl2 solvent ruthenium(II) (E ) N, P) complexes are presented in Scheme
molecules of crystallization at 0.5, 0.5, 0.5 could be refined. Therefore, 1. Relevant spectroscopic data for the complexes are given in
its contribution in the structure factor calculations was taken into Tables 2 and 3.
account using the PLATON/SQUEEZE25,26 method. Hydrogen atoms Synthesis of [mer,trans-RuCl2(NN′N)(PPh3)] (1) and [mer-
were taken into account at calculated positions. ,trans-RuCl2(PNP)(PPh3)] (2). The dichloride complex [RuCl2-
[mer-RuCl(MeCN)(NN′N)(PPh3)]OTf (6a). A total of 16 898 (NN′N)(PPh3)] (1) is conveniently prepared by a ligand
reflections (θmax ) 25.4°) were scanned and averaged into a unique exchange reaction of [RuCl2(PPh3)3] with a stoichiometric
set of 16 116 reflections (11 985 with I > 2σ(I)). The structure was amount of NN′N in CH2Cl2. The complex is a yellow-brown
solved by direct methods (SHELXS8627) and refined on F2 with
solid, stable in both the solid state and in oxygen-free solutions.
SHELXL93.24 Disordered solvents (CHCl3) were taken into account
using PLATON/SQUEEZE.25,26 Hydrogen atoms were taken into The retention of one PPh3 ligand in 1 is clearly shown by
account at calculated positions. elemental analysis and NMR spectroscopy. In principle, the
[(µ-N2)(mer,trans-RuCl2(NN′N))2] (8). A total of 19 600 reflections octahedral complex 1 has four stereoisomers. In addition to
(θmax ) 27.5°) were scanned and averaged into a unique set of 7205 one trans-dichloro isomer, the cis-dichloro isomer may exist in
reflections (6402 with I > 2σ(I)). The structure was solved by direct three diastereomeric forms with mer or fac arrangement of the
methods (SHELXS8627) and refined on F2 with SHELXL96.28 Dis- NN′N donor atoms, made possible by the flexibility of the
ordered diethyl ether was handled with the PLATON/SQUEEZE25,26 o-CH2NMe2 substituents (Chart 1).
technique. Hydrogen atoms were taken into account at calculated The 1H and 31P NMR spectra of 1 show a single resonance
positions. pattern at all temperatures for all nuclei, indicating the presence
[mer-RuCl(CO)(NN′N)(PPh3)]OTf (11). A total of 9670 reflections of a single stereoisomer in solution. Singlet resonances are
(θmax ) 27.5°) were scanned and averaged into a unique set of 9571
observed for the benzylic protons as well as for the NMe2
reflections (6554 with I > 2σ(I)). The structure was solved by Patterson
methods (DIRDIF23) and refined on F2 with SHELXL96.28 One of groups, which point to homotopic benzylic protons and NMe2
the SO3CF3 ions is heavily disordered and was taken into account along groups, respectively. Moreover, the 31P{1H} NMR shows one
with the disordered solvent with the PLATON/SQUEEZE25,26 technique. high-field singlet resonance for PPh3 at 37.0 ppm. This is a
Hydrogen atoms were taken into account at calculated positions. The characteristic chemical shift for coordinated PPh3 trans to a
racemic twin parameter refined to 0.41(6). neutral donor ligand. These observations rule out the cis
[mer-RuOTf(CO)(NN′N)(HOEt)]OTf (13). A total of 4100 reflec- stereoisomers III and IV (of Chart 1) having a fac arrangement
tions (θmax ) 27.5°) were scanned and averaged into a unique set of but are in agreement with a mer,trans-I structure, analogous to
3036 reflections (2982 with I > 2σ(I)). The structure was solved by that established for [RuCl2(terpy)(PPh3)] (terpy ) 2,2,6:2′′-
terpyridine).30 Of the latter complex, both the mer,trans and
(23) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; Garcia- the mer,cis isomers can be synthesized.30 The quantitative
Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykala, C. The DIRDIF96
Program System; Technical Report of the Crystallographic Laboratory, formation of [mer,cis-RuCl2(terpy)(PPh3)] by a direct ligand
Universiteit of Nijmegen: Nijmegen, The Netherlands, 1996. exchange reaction of RuCl2(PPh3)3 with terpy in benzene at
(24) Sheldrick, G. M. SHELXL93. Program for Crystal Structure Refine- reflux for 1 h has been reported.30 However, the analogous
ment; University of Göttingen: Göttingen, Germany, 1993. reaction with NN′N results in an almost quantitative formation
(25) Spek, A. L. Am. Cryst. Assoc. Abstr. 1994, 22, 66.
(26) Spek, A. L. Acta Crystallogr. 1987, C43, 1233-1235.
(27) Sheldrick, G. M. SHELXS86. Program for Crystal Structure Solution; (29) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl.
University of Göttingen: Göttingen, Germany, 1986. Crystallogr. 1993, 26, 343-350.
(28) Sheldrick, G. M. SHELXS96. Program for Crystal Structure Solution; (30) Sullivan, B. P.; Calvert, J. M.; Meyer, T. J. Inorg. Chem. 1980, 19,
University of Göttingen: Göttingen, Germany, 1996. 1404-1407.
16- and 18-Electron Ru(II) Complexes of NN′N Inorganic Chemistry, Vol. 37, No. 8, 1998 1753

Scheme 1. Reaction Routes to RuII[ENE] Complexes

Table 2. Relevant 1H, 31P, and UV/Vis Data for NN′N-RuII Complexesa
1H NMRa,b 31P NMRa,c UV/visd
complex NMe2 CH2e p-HNN′N f PPh3 λmax ()
NN′N 2.20 3.50 7.54
1 2.10 4.00 7.65 37.0 390 (4949)
3g 2.68, 2.32 4.05, 3.51 (16) h 86.6 365 (11 144), 530 (3500)
4 2.71, 2.31 3.95, 3.21 (16) 7.75 74.5 342 (5532), 508 (1691)
6a 2.37, 2.11 4.30, 3.89 (15) 7.87 32.8 350 (4663)
7i 2.20 4.14 8.10 37.4 282 (5933)
a In CDCl at 298 K (unless stated otherwise). b 300 MHz. Chemical shift values (δ, ppm) indirectly referenced to SiMe using solvent signals.
3 4
c81 MHz. Chemical shift values (δ, ppm) are relative to 85% H3PO4 with positive values being downfield from the standard. d In CH2Cl2, λmax in
nm;  in L mol-1 cm-1. e 2JHAHB (Hz) given in parentheses. f Triplet. g Acetone-d6. h Not isolated. i DMSO-d6.

Table 3. Relevant 13C NMR Data for NN′N-RuII Complexesa

NN′N PPh3
complex CH2 NMe2 Cortho Cmeta Cpara Cipsob Corthoc Cmetad Cpara
NN′N 65.8 45.6 158.5 121.2 136.6
1 73.7 55.6 161.7 119.3 135.0 138.9 (31.7) 127.5 (8.3) 134.4 (9.2) 128.3
3e 73.7 52.8, 47.6 162.7 122.6 137.3 134.3 (51.9) 129.2 (10.5) 134.4 (9.9) 131.2
4 72.1 52.6, 45.7 162.6 122.6 137.8 131.6 (46.1) 128.9 (10.6) 133.4 (9.6) 131.3
6a 73.6 55.1, 55.7 159.6 121.0 137.8 136.1 (35.5) 128.6 (8.8) 133.0 (9.6) 129.4
7f 75.1 57.2 161.4 123.9 141.8 136.5 (37.9) 131.6 (9.4) 135.0 (9.8) 132.5
a
75.469 MHz, CDCl3 at 298 K (unless stated otherwise). Chemical shift values (δ, ppm) indirectly referenced to SiMe4 using solvent signals.
b 1J
PC given in parentheses. c 2J(P,C) given in parentheses. d 3JPC given in parentheses. e Acetone-d6. f DMSO-d6.
of [mer,trans-RuCl2(NN′N)(PPh3)] (1) only. No mer,cis product [RuCl2(PNP)(PPh3)] (2) was obtained.7d Also, the 1H NMR
is formed according to the 31P{1H} NMR spectrum. The crystal spectrum of 2 shows a singlet resonance for the benzylic protons
structure of 1 (Figure 2) also reveals this mer,trans configuration. indicating again a meridional coordination mode of the PNP
Some selected crystallographic data for 1 are summarized in ligand with trans-positioned chloride ligands. Moreover, the
Table 4. 31P{1H} NMR spectrum of 2 shows a set of a doublet and a

In contrast to RuCl2(PPh3)3, RuCl2(PMe3)4 does not react with triplet resonance with a coupling constant of 29 Hz which is
the NN′N ligand at room temperature in CH2Cl2. Obviously, characteristic for a MX2Y ligand system and is independent
the PMe3 ligands are too strongly bound to ruthenium(II) for a proof for the cis arrangement of PPh3 and the phosphine
ligand exchange reaction to take place. Accordingly, PMe3 was substituents of the PNP ligand.
found to react with complex 1 with dissociation of both NN′N Reaction of 1 with Silver Triflate, Preparation of [RuCl-
and less basic31 PPh3 to RuCl2(PMe3)4. (NN′N)(PPh3)]OTf (3) and [RuOTf(NN′N)(PPh3)]OTf (4).
Using the same type of ligand exchange reaction of RuCl2- When a solution of complex 1 in CH2Cl2 is reacted with either
(PPh3)3 with PNP, the structurally closely related complex 1 or 2 equiv of AgOTf, purple complexes RuCl(OTf)(NN′N)-
(PPh3) (3) and Ru(OTf)2(NN′N)(PPh3) (4), respectively, are
(31) Basicity of phosphines:32 PPh3, pKa ) 2.73; PMe3 ) 8.65.
(32) Henderson, W. A., Jr.; Streuli, C. A. J. Am. Chem. Soc. 1960, 82, obtained. The 19F{1H} NMR spectrum of 4 in CDCl3 at 300
5791-5794. K, shows two distinct singlet resonances at -77.82 and -78.17
1754 Inorganic Chemistry, Vol. 37, No. 8, 1998 Abbenhuis et al.

chemistry, and only a limited number of ruthenium complexes

with such anions have been reported.34 The molecular structure
of the [RuOTf(NN′N)(PPh3)] cation shows a five-coordinate
square-pyramidal ruthenium(II) center with one η1-O bonded
triflate anion. The five-coordinate square-pyramidal structure
of the cation of 4 is distorted to a trigonal bipyramidal one by
a 77% movement along the Berry pseudorotation axis toward
the latter.35 The cationic nature, as well as the square-pyramidal
geometry of the [4]+ cation of 4 found in the solid state, is also
consistent with the solution NMR data. In [4]+ the NN′N ligand
functions as a terdentate ligand system that occupies three
positions in the basal plane of the square pyramid; the N(2)-
Ru-N(3) angle is 150.7(2)°. The η1-bonded triflate occupies
the other basal position (∠N(1)-Ru-O(1) ) 168.50(20)°),
while the PPh3 is coordinating apically (∠N(1)-Ru-P ) 95.50-
(18)°). Interestingly, the monocation [4]+ is isostructural with
the neutral 16-electron Ru-NCN complex [RuI(NCN)(PPh3)]
Figure 2. Thermal motion ellipsoid plot (50% probability level) of 1. (5).10 However, the ruthenium-phosphine distance in the solid
H atoms are omitted for clarity.
state structure of 5 (2.1757(7) Å) is lengthened significantly to
Chart 1. Potential Coordination Modes of NN′N in 2.212(2) Å in the monocation of 4, pointing to a weaker Ru-P
RuII[NN′N] Complexes interaction in [4]+. On first sight, this is surprising as one would
expect the cationic ruthenium center in [4]+ to have a higher
Lewis acidity than the Ru in 5 due to the presence of the
monoanionic (NCN) ligand in the latter. Although it is difficult
to evaluate the possible influence of the difference in anionic
character of iodine and triflate, these results seem to indicate
that the [NCN]- ligand (in 5) is a weaker σ-donating ligand as
compared with NN′N (in 4). However, when compared to the
Ru-P bond lengths of 2.337(3) and 2.3451(12) Å in the six-
coordinate complexes 1 and 6a, respectively, the Ru-P distance
in 4 is considerably shortened (2.212(2) Å). Obviously, the
ruthenium center in the five-coordinate 4 has a higher Lewis
acidic character as compared to both six-coordinate complexes
1 and 6a. Moreover, the Lewis acidic character of the six-
coordinate complexes 1 and 6a is comparable, despite the
ppm. The signal at -78.17 ppm has been assigned to a free
cationic character of the latter.
triflate anion;33 this is supported by the observation that the 19F
NMR signal of [Bu4N]OTf in CDCl3 under the same conditions Preparation and Characterization of [mer-RuCl(MeCN)-
occurs at -78.27 ppm. The 19F NMR spectrum of RuCl(OTf)- (NN′N)(PPh3)]OTf (6) and [mer,trans-Ru(MeCN)2(NN′N)-
(NN′N)(PPh3) in acetone-d6 shows only one signal for free (PPh3)]OTf2 (7). The chloride ligands in complex 1 can be
triflate anion at -77.76 ppm ([Bu4N]OTf: -77.73 ppm). These readily substituted for acetonitrile molecules when a solution
observations lead to the conclusion that these complexes can of 1 in dichloromethane is treated with 1 or 2 equiv of AgOTf
be best described as cationic 16-electron species [RuCl(NN′N)- in the presence of MeCN. In this way, the complexes with the
(PPh3)]OTf (3) and [RuOTf(NN′N)(PPh3)]OTf (4) respectively. stoichiometry [RuCl(OTf)(NN′N)(MeCN)(PPh3)] (6a) and [Ru-
The 1H NMR spectra of both 3 and 4 consist of a characteristic (OTf)2(NN′N)(MeCN)2(PPh3)] (7) were obtained as light yellow
AX pattern for the benzylic protons and two distinct resonances solids. The 19F{1H} NMR spectrum of 6 in CDCl3 shows one
for the NMe2 groups, indicating C2V symmetry in the complexes. singlet resonance at -78.26 ppm, corresponding to free triflate
Moreover, the 31P{1H} NMR spectra of both 3 and 4 show a anion (Vide infra). Moreover, the 19F NMR spectrum of 7 also
sharp singlet resonance at relatively low field (δ ) 85.6 and shows one singlet resonance for free triflate ion at -77.15 ppm
74.7 ppm, respectively), which is characteristic for a deshielded ([Bu4N]OTf: -77.17 ppm). These observations point to the
PPh3 donor. Such low-field resonances of PPh3 have also been formation of mono- and dicationic complexes of type [RuCl-
observed for the related five-coordinate, neutral 16-electron (MeCN)(NN′N)(PPh3)]OTf (6a) and [Ru(MeCN)2(NN′N)(PPh3)]-
ruthenium(II) complexes [RuCl(NCN)(PPh3)] and [RuI(NCN)- OTf2 (7), respectively. The proton NMR spectrum of 6a (in
(PPh3)] (5) (δ ) 91.1 and 89.0 ppm, respectively10) containing CDCl3) shows an AX resonance pattern for the benzylic protons
the terdentate, monoanionic [C6H3(CH2NMe2)2-2,6]- ([NCN]-) and two distinct singlet resonances for NMe2 units, indicating
ligand. The structural description of these complexes in solution that the benzylic carbons and the nitrogen atoms of the NMe2
is similar to their structure in the solid state. units lie in a molecular plane of symmetry. In the 31P{1H} NMR
Suitable crystals of 4 were grown from a CH2Cl2 solution spectrum, a singlet resonance appears at 32.8 ppm which is
layered with pentane. The solid state structure of 4 (Figure 3) illustrative for triphenylphosphine coordinating trans to the
clearly shows the separation of cation and anion. Some selected pyridine nitrogen.
crystal data are summarized in Table 4. The η1-bonding mode
of the triflate anion is rather unusual in ruthenium coordination (34) (a) Blosser, P. W.; Gallucci, J. C.; Wojcicki, A. Inorg. Chem. 1992,
31, 2376. (b) Kraakman, M. J. A.; De Klerk-Engels, B.; De Lange, P.
P. M.; Vrieze, K.; Spek, A. L. Organometallics 1992, 11, 3774.
(33) Hollis, T. K.; Robinson, N. P.; Bosnich, B. Organometallics 1992, (35) Holmes, R. R. Prog. Inorg. Chem. 1984, 32, 119 and references cited
11, 2745-2748. therein.
16- and 18-Electron Ru(II) Complexes of NN′N Inorganic Chemistry, Vol. 37, No. 8, 1998 1755

Table 4. Selected Bond Distances (Å) and Angles (deg) for Complexes 1, 4, 6a, 11, and 13
1 4 6a 11 13
Bond Distances
Ru1-N1 2.023(8) 1.953(7) 2.024(4) 2.058(7) 1.973(2)
Ru1-N2 2.229(10) 2.143(6) 2.226(4) 2.230(7) 2.188(3)
Ru1-N3 2.211(8) 2.151(6) 2.222(4) 2.201(6) 2.177(3)
Ru1-P1 2.337(3) 2.212(2) 2.3451(12) 2.2384(2) -
Ru1-Cl1 2.421(3) - 2.4060(14) 2.445(2) -
Ru1-Cl2 2.429(3) - - - -
Ru1-OSO2 - 2.141(6) - - 2.143(2)
Ru1-HOEt - - - - 2.159(2)
Ru1-N4 - - 1.996(4) - -
Ru1-CO - - - 1.851(8) 1.815(3)
Bond Angles
N2-Ru1-N3 155.8(3) 150.7(2) 156.16(14) 157.1(3) 160.65(9)
N1-Ru1-N2 77.9(3) 81.3(2) 78.00(16) 78.3(3) 80.19(13)
N1-Ru1-N3 78.0(3) 79.7(3) 78.18(16) 78.7(3) 80.55(13)
Cl1-Ru1-C12 174.48(8) - - - -
Cl1-Ru1-N1 84.7(3) - 89.53(11) 87.70(19) -
Cl1-Ru1-N2 92.8(3) - 93.13(10) 93.0(2) -
Cl1-Ru1-N3 86.8(3) - 87.70(10) 86.32(16) -
Cl1-Ru1-N4 - - 175.89(11) - -
N1-Ru1-P1 175.9(3) 95.50(18) 177.67(11) 178.97(19) -
N2-Ru1-P1 102.0(2) 103.97(16) 101.91(10) 101.9(2) -
N3-Ru1-P1 102.1(2) 99.92(18) 101.84(10) 101.1(2) -
P1-Ru1-OSO2 - 94.27(16) - - -
N1-Ru1-OSO2 - 168.5(2) - - 170.07(11)
Cl1-Ru1-CO - - - 177.3(3) -
EtOH-Ru1-CO - - - - 176.78(12)
N1-Ru1-CO - - - 89.6(3) 94.31(13)
N2-Ru1-CO - - - 86.7(3) 93.68(13)
N3-Ru1-CO - - - 92.9(3) 89.48(13)

Figure 4. Thermal motion ellipsoid plot (50% probability level) of

6a. H atoms are omitted for clarity.
Figure 3. Thermal motion ellipsoid plot (50% probability level) of 4. The lability of chloride in complex 1 is clearly demonstrated
H atoms are omitted for clarity. by its reaction with acetonitrile in the absence of silver triflate.
The solid state molecular structure of 6a (Figure 4) shows When a suspension of 1 in acetonitrile is gently heated at 55
meridional coordination of NN′N with the chloride and MeCN °C for a few minutes, a clear brown solution is formed, which,
ligand in apical positions and a PPh3 trans-positioned relative after evaporation of MeCN, yields a yellow-brown solid with
to the pyridine nitrogen. Some selected bond distances and molecular formula [RuCl2(MeCN)(NN′N)(PPh3)] (6b) in almost
angles are given in Table 4. quantitative yield. The 13C and 31P NMR spectra of this new
The NMR data for complex 7 indicate a high degree of complex closely resemble those of the monocationic complex
symmetry within a complex cation; in its 1H NMR spectrum 6a; however, the 1H NMR spectrum in CDCl3 differs. Although
(DMSO-d6) the NN′N ligand shows singlet resonances for the the resonances arising from the pyridine and PPh3 units are quite
four methylene protons and for the methyl groups of the NMe2 similar, the singlet resonance of coordinated MeCN is shifted
units. It also reveals the presence of two coordinating MeCN to higher field (from 1.91 ppm in 6a to 2.15 ppm in 6b). Along
ligands. The 31P{1H} NMR spectrum of complex 7 shows, like with this, the chemical shifts of the doublet resonances of the
those of 1 and 6a, a high-field singlet resonance (37.4 ppm). AX pattern of the benzylic protons are significantly shifted (from
These data suggest a simple trans,mer-I (see Chart 1) octahedral 4.30 and 3.88 ppm for 6a to 4.33 and 4.12 ppm). Upon
geometry at the dicationic metal, with NN′N coordinating exchange of one chloride anion for one triflate anion by reaction
meridionally. of 6b with 1 equiv of AgOTf, the 1H NMR spectrum of the
1756 Inorganic Chemistry, Vol. 37, No. 8, 1998 Abbenhuis et al.

product becomes identical with that of 6a. The UV/visible Table 5. Selected Bond Distances (Å) and Angles (deg) for
spectrum of 6b in dichloromethane closely matches the spectrum Complex 8
of 6a. Both complexes show an absorption maximum at the Bond Distances
same wavelength (350 nm) along with an extinction coefficient Ru1-N11 1.9695(19) Ru2-N21 1.969(2)
of about 4600, proving that both complexes must be isostructural Ru1-N12 2.166(2) Ru2-N22 2.172(2)
and that 6b can be described as [RuCl(MeCN)(NN′N)(PPh3)]- Ru1-N13 2.169(2) Ru2-N23 2.177(2)
Ru1-Cl11 2.4121(7) Ru1-Cl21 2.4223(7)
Cl. We believe that the differences observed in the 1H NMR Ru1-Cl12 2.4202(6) Ru2-Cl22 2.4233(7)
spectra arise from differences in the anion-cation pair associa- Ru1-N14 1.9562918) Ru2-N24 1.953(2)
tions in CDCl3 solution.7d N14-N24 1.110(3)
During the reaction of 1 with acetonitrile at 55 °C, no Bond Angles
formation of dicationic [Ru(MeCN)2(NN′N)(PPh3)]2+, analogous N11-Ru1-N12 80.48(9) N21-Ru2-N22 80.37(9)
to 7, is observed. At reflux conditions, besides the formation N11-Ru1-N14 177.07(8) N21-Ru2-N24 177.83(8)
of 6b, partial dissociation of triphenylphosphine from 1 is N12-Ru1-N13 161.61(9) N22-Ru2-N23 160.07(9)
observed along with the formation of unidentified side products. Cl11-Ru1-Cl12 178.71(2) Cl21-Ru3-Cl22 177.07(3)
Ru1-N14-N24 172.75(18) Ru2-N24-N14 174.10(18)
From 1H NMR spectra, crystalline samples of 6b proved to
contain non-coordinating CH2Cl2. Attempts to obtain a CH2- performed. Some selected bond distances and angles are
Cl2-free sample of 6b by heating powdered crystals of 6b‚xCH2- collected in Table 5. The solid state structure of the product
Cl2 in Vacuo at 80 °C overnight failed because of partial (Figure 5) shows two RuCl2(NN′N) moieties, which are
dissociation of MeCN and re-formation of 1. symmetrically bridged by molecular nitrogen. Both NN′N
Unexpected Formation of (µ-Dinitrogen)({mer,trans-RuCl2- ligands are coordinating meridonally, with a resulting trans-
(NN′N}2) (8). When a slurry of polymeric [RuCl2(nbd)]n (nbd positioning of the chloride ligands.
) 2,5-norbornadiene) is reacted with the NN′N ligand in On basis of this data, the complex can be formulated as [(µ-
refluxing benzene under a dinitrogen atmosphere, a yellow- N2){mer,trans-RuCl2(NN′N)}2] (8, Scheme 2). The NN′N
brown reaction mixture is obtained from which, after workup, ligands are twisted in such a way that the planes defined by
light reddish-brown crystals of a new ruthenium complex are N(11)N(14)Cl(11)Cl(12) and N(21)N(24)Cl(21)Cl(22) are ori-
obtained which readily turn green upon exposure to air. 1H as entated almost perpendicularly, the actual angle being 89.38-
well as 13C NMR analyses of this crystalline product showed (5)°. Moreover, the Ru(1)-N(14)-N(24)-Ru(2) bonding unit
only singlet resonances for the benzylic protons and NMe2 units, is slightly bent, as indicated by the dihedral angle of Ru(1)N-
pointing to a meridionally coordinating NN′N ligand. Assuming (14)N(24)Ru(2) of 6(3)°. The N(14)-N(24) distance is 1.110-
the presence of a RuCl2 fragment, it was anticipated that the (3) Å (cf. N-N ) 1.0977 Å for free N241); consistent with back-
chloride ligands are trans-positioned as observed in the com- donation of electron density from RuII to N2.39c A comparable
plexes 1 and 2. According to elemental analysis, C/H and C/N lengthening of the NtN distance to 1.124 Å was also observed
ratios were consistent with a product with molecular formula for the closely related tetracationic dimer [(NH3)5Ru(N2)Ru-
[N2Ru2Cl4(NN′N)2], i.e. of two RuCl2(NN′N) moieties and one (NH3)5][(BF4)4].39c The almost perpendicular twisting of the
molecule of N2. However, the analyzed values of both carbon, two NN′N ligand systems in complex 8 can be accounted for
hydrogen, and nitrogen were consistently lower than the ones by a simple orbital argument. As Ru2+ is a 6-electron metal
calculated. Transition metal complexes containing dinitrogen ion in an octahedral coordination sphere, the t2g set of orbitals
as a ligand have been extensively studied36 in view of their is filled. Therefore, π back-donation of electron density from
relevance to nitrogen fixation.37 In fact, the dinitrogen metal ruthenium t2g orbitals will occur into two orthogonal sets of
complex [(N2)Ru(NH3)5]2+, Allen and Senoff’s ion,38 was the empty π* antibonding orbitals of the nitrogen. By perpendicular
first stable transition metal-dinitrogen complex synthesized, twisting of the RuCl2(NN′N) moieties, this back-donation will
and it shows a characteristic νNtN vibration. However, in the be optimally effective.
IR spectrum of the new complex, no stretching vibration νNtN Reactions of 3 and 4 with CO. In view of the expected
is observed, which suggests that this complex has a symmetric reactivity of our 16-electron, coordinatively unsaturated com-
dimeric structure with a µ2-bridging dinitrogen molecule. plexes 3 and 4 toward potential substrates, we have carried out
Indeed, in the Raman spectrum a strong signal for a N-N some reactions with CO.
stretching vibration at 2099 cm-1 is found, proving the presence When CO is bubbled through a purple solution of the chloride
of a bridging dinitrogen ligand. Support for this assignment is complex [RuCl(NN′N)(PPh3)]OTf (3) in CH2Cl2, the color
provided by the vibrational data of the tetracationic complexes changes from purple to light brown. Upon addition of pentane,
[(NH3)5Ru(N2)Ru(NH3)5][(BF4)4] (2100 cm-1) and [(NH3)5Ru- a yellow precipitate, consisting mostly of [RuCl(CO)2(NN′N)]-
(N2)Ru(H2O)5][(BF4)4] (2080 cm-1).39c,40 OTf (10), is obtained. The presence of two coordinating CO
To obtain conclusive evidence about the nature of the ligands in this complex was clearly established by both 13C
crystalline product, a single crystal X-ray determination was NMR and IR spectroscopy. The 13C NMR spectrum of 10
shows two CO resonances, and in the νCO region of the IR
(36) (a) Hidai, M.; Mizobe, Y. Chem. ReV. 1995, 95, 1115-1133. (b) Leigh, spectrum two absorptions are observed, pointing to a complex
G. J. Acc. Chem. Res. 1992, 25, 177-182. of type cis-L4M(CO)2.42 The 1H NMR spectrum of 10 shows
(37) See for example: Gambarotta, S. J. Organomet. Chem. 1995, 500
(1-2), 117-126. a characteristic AB pattern for the benzylic protons as well as
(38) Allen, A. D.; Senoff, C. V. J. Chem. Soc., Chem. Commun. 1965, two distinct resonances for the NMe2 units of the NN′N ligand,
621-622. characteristic for meridionally coordinating NN′N together with
(39) (a) X-ray: Treitel, I. M.; Flood, M. T.; Marsh, R. E.; Gray, H. B. J.
Am. Chem. Soc. 1969, 91, 6512-6513. (b) Raman spectroscopy: a cis-orientation of the two CO ligands.
Chatt, J.; Nikolsky, A. B.; Richards, R. L.; Sanders, J. R. J. Chem.
Soc., Chem. Commun. 1969, 154-155. (c) MO description: On- (41) Handbook of Chemistry and Physics, 76th ed.; Lide, R. D., Ed.; CRC
drechen, M. J.; Ratner, M. A.; Ellis, D. E. J. Am. Chem. Soc. 1981, Press: New York, 1995; Section 9, p 20.
103, 1656-1659. (42) Cotton, F. A.; Wilkinson, G. AdVanced Inorganic Chemistry, 5th ed.;
(40) Creutz, C.; Taube, H. Inorg. Chem. 1971, 10, 2664. Wiley: New York, 1988; p 1034.
16- and 18-Electron Ru(II) Complexes of NN′N Inorganic Chemistry, Vol. 37, No. 8, 1998 1757

Figure 5. Thermal motion ellipsoid plot (50% probability level) of 8. H atoms are omitted for clarity.

Scheme 2

Interestingly, when pentane is allowed to slowly diffuse into

the reaction mixture, a compound with molecular formula
[RuCl(CO)(NN′N)(PPh3)]OTf (11) crystallizes in high yield.
The 1H NMR spectrum of this complex showed diastereotopic
resonances of benzylic protons and NMe2 units, indicating a
molecular geometry involving meridional terdentate NN′N
coordination. The presence of one coordinating CO was
established by 13C NMR and IR spectroscopy. The 13C NMR
spectrum showed only one carbonyl signal, with a small 2JPC
coupling constant of 13.6 Hz, pointing to a mutual cis-position Figure 6. Thermal motion ellipsoid plot (50% probability level) of
of CO and PPh3. In the νCO region of the IR spectrum also 11. H atoms are omitted for clarity.
only one signal was observed. In order to establish the Scheme 3
stereochemistry of 11 and to obtain information about relevant
bond angles and distances in the solid state, a single crystal
X-ray determination was performed (Figure 6 and Table 4).
The mechanism of formation of 10 most probably involves
the addition of one molecule of CO to the coordinatively
unsaturated 16-electron complex 3, followed by rearrangement
of the intermediate through Berry-pseudorotation intermediates
to 11. Subsequent substitution of the PPh3 ligand by CO then into the nature of the Ru-OTf bond. When CO is bubbled
affords 10 (Scheme 3). This type of reactivity has also been through a purple solution of 4 in CH2Cl2, a color change from
observed in structurally closely related neutral ruthenium(II) purple to yellow is observed. Independent of the mode of
complexes containing the monoanionic ligands [C6H3(CH2- addition of pentane to the reaction mixture, a precipitate is
NMe2)2-2,6]- ([NCN]- and [C6H3(CH2PPh2)2-2,6]- ([PCP]-).10,11 formed existing of at least four unidentified products. The
For example, reaction of [RuCl(ECE)(PPh3)] with CO yields yellow color of these products points to the formation of
neutral complexes of type [RuCl(CO)2(ECE)] with cis- coordinatively saturated 18-electron complexes. From NMR
positioned CO ligands, as in 10. The formation of these analyses of this impure yellow solid, it could be concluded that
complexes also proceeds Via a neutral monocarbonyl [RuCl- no dissociation of the NN′N ligand has taken place. The
(CO)(ECE)(PPh3)] intermediate analogous to 10.43 presence of AX resonance patterns in the 1H NMR spectrum
The reaction of the triflate complex [RuOTf(NN′N)(PPh3)]- points to meridionally coordinating NN′N in all of the newly
OTf (4) with CO was of interest because it could give insight formed complexes. One of the products formed (in 10-30%
yield) is the monocarbonyl complex [mer-RuOTf(CO)(NN′N)-
(43) Karlen, T.; Veldman, N.; Spek, A. L.; van Koten, G. Manuscript in (PPh3)]OTf (12). However, all attempts to isolate a pure product
preparation. Via crystallization failed. Obviously, upon changing from X
1758 Inorganic Chemistry, Vol. 37, No. 8, 1998 Abbenhuis et al.

the five-membered chelate rings Ru-N(1)-C-C-N(2) and

Ru-N(1)-C-C-N(3) is partially released by ring puckering,
which is of C2 symmetry, placing one amino methyl group
axially on each side of the plane defined by the pyridine ring.
The flexibility of the nitrogen donor substituents of the NN′N
ligand is clearly demonstrated in the 16-electron complex 4. In
this complex, the five-membered chelate rings are puckered with
mirror plane symmetry (see plane through C(4)NRuO(1) and
P(1)). Consequently in this structure, one of the methyl groups
of each NMe2 unit is axially positioned, and these reside at the
same side of the pyridine plane. As a result the remaining NMe
groups are in equatorial position. This structural motif has also
been observed in the solid state structure of the related
pentacoordinated complex [RuOTf(NCN)(PPh3)].10 However,
in contrast to complexes containing the [NCN]- ligand,10 no
facial coordination of the NN′N ligand is found. Although
Figure 7. Thermal motion ellipsoid plot (50% probability level) of bidentate coordination of terpyridine has been reported,44
13. H atoms are omitted for clarity. bidentate coordination of NN′N has so far not been observed
either.
Scheme 4
Conclusions
Although the NN′N ligand system bears some resemblance
to the more rigid terpyridine, complexes containing the NN′N
ligand are not restricted to six-coordination. The NN′N ligand
forms well-defined, five- and six-coordinate Ru(II) complexes
Scheme 5 (16- and 18-electron species, respectively) in combination with
a variety of unidentate ligands. In all complexes obtained so
far, NN′N uses all three nitrogen donor atoms to coordinate to
the metal center in a rather flexible coordination mode. The
structural feature of five-coordination results in the formation
of coordinatively unsaturated ruthenium(II) complexes contain-
ing the NN′N ligand and makes these complexes interesting
) chloride in 3 to X ) triflate in 4, no change of stereoselec- from the viewpoint of potential application in homogeneously
tivity in the initial reaction with CO is observed. In both cases, ruthenium(II)-catalyzed reactions. The presence of a labile
the intermediate monocarbonyl product is formed. However, dinitrogen ligand makes complex 8 potentially interesting as a
as stated above, only in the case where X ) Cl a pure dicarbonyl precursor for the synthesis of a variety of ruthenium(II)
product could be isolated. It is noteworthy that the structurally complexes of type RuCl2(NN′N)L, where L is a neutral ligand.
related neutral complex [RuOTf(PCP)(PPh3)] has been reported We have already found that the dinitrogen can be readily
to be converted into [trans-Ru(PCP)(CO)2(PPh3)] upon reaction replaced by small molecules like ethylene,45 and we are currently
with CO.43 investigating this reactivity further.
Remarkably, when the same reaction of [RuOTf(NN′N)-
(PPh3)]OTf (4) with CO is performed in the presence of ethyl Acknowledgment. R.A.T.M.A. thanks the Dutch Depart-
alcohol (Scheme 4), upon slow diffusion of pentane in the ment of Economic Affairs in terms of the Innovative Oriented
reaction mixture, large orange to yellow crystals are obtained Research Program Catalysis (IOP-Katalyse) for financial sup-
of which the IR spectrum shows only one resonance in the area port. This work was supported in part (A.L.S.) by the Nether-
of the νCO absorption frequency, pointing to the presence of lands Foundation for Chemical Research (SON) with financial
only one CO ligand. 1H NMR spectroscopy in acetone-d6 or aid from the Netherlands Organization for Scientific Research
DMSO-d6 revealed the presence of one molecule of ethanol in (NWO). Mr. W. J. J. Smeets and Mr. D. Kruis are acknowledged
the product. However, due to partial or complete dissociation for performing X-ray crystallographic studies. I.d.R. thanks the
of the complex in the potentially coordinating solvents used, EU for financial support under Grant No. ERBFMBICT961634.
no NMR data could be obtained. According to elemental Mr. E. T. Lutz is kindly acknowledged for recording Raman
analysis, the product can be formulated as [RuOTf(CO)(NN′N)- spectra.
(HOEt)]OTf (13). The solid state structure of 13 (Figure 7)
Supporting Information Available: Two tables of NMR data for
shows an octahedrally coordinated ruthenium(II) center with the tridentate ligands (1 page). X-ray crystallographic files in CIF
meridionally coordinating NN′N. The axial positions are format for the structure determinations of complexes 1, 4, 6a, 8, 11,
occupied by the ethyl alcohol and the CO ligand. The anionic and 13 are available in the Internet only. Ordering and access
triflate ligand is trans-positioned toward the central pyridine information is given on any current masthead page.
atom. Some structural data of complex 13 (Scheme 5) are
IC971061+
collected in Table 4.
Coordination Behavior of NN′N. In the octahedral 18-
electron complexes 1, [6]X, 7, 8, and 13, the NN′N ligand (44) Deacon, G. B.; Patrick, J. M.; Skelton, B. W.; Thomas, N. C.; White,
A. H. J. Aust. Chem. 1984, 37, 925.
system is meridionally bonded with the ruthenium center lying (45) del Rı́o, I.; Gossage, R. A.; van Koten, G. Eur. J. Inorg. Chem.,
in the plane defined by the pyridine ring. The ring strain in submitted.