DOI: 10.1002/chem.
201503404 Communication
& Boron Chemistry
New Routes to a Series of s-Borane/Borate Complexes of
Molybdenum and Ruthenium
Rongala Ramalakshmi,[a] Koushik Saha,[a] Dipak Kumar Roy,[a] Babu Varghese,[b]
Ashwini K. Phukan,[c] and Sundargopal Ghosh*[a]
lationship between alkane and monoborane Lewis base ad-
Abstract: A series of agostic s-borane/borate complexes ducts, Shimoi and co-workers synthesized and investigated the
have been synthesized and structurally characterized from stability of the M¢H¢B bond in various borane s-complexes
simple borane adducts. A room-temperature reaction of stabilized by Lewis base adducts.[6] Subsequently, Sabo-Etienne
[Cp*Mo(CO)3Me], 1 with Li[BH3(EPh)] (Cp* = pentamethyl- and co-workers isolated an agostic ruthenium complex,
cyclopentadienyl, E = S, Se, Te) yielded hydroborate com- [RuH2{h2-H-B(NiPr2)CH2PPh2}(PCy3)2] by using polyhydride ruthe-
plexes [Cp*Mo(CO)2(m-H)BH2EPh] in good yields. With nium complexes and a potentially hemilabile boron-containing
2-mercapto-benzothiazole, an N,S-carbene-anchored ligand.[7] Many additional attempts to address this problem by
s-borate complex [Cp*Mo(CO)2BH3(1-benzothiazol-2-yli- synthesis of various s-borane/borate complexes have been
dene)] (5) was isolated. Further, a transmetalation of the made.[11]
B-agostic ruthenium complex [Cp*Ru(m-H)BHL2] (6, L = As part of our interest in the synthesis of electron-precise
C7H4NS2) with [Mn2(CO)10] affords a new B-agostic com- transition-metal–boron complexes,[12] we recently reported sev-
plex, [Mn(CO)3(m-H)BHL2] (7) with the same structural eral triple-bridged borylene, boryl, and diborane mole-
motif in which the central metal is replaced by an isolobal cules.[12, 13] Progressively, more multimetallic boron complexes
and isoelectronic [Mn(CO)3] unit. Natural-bond-orbital containing a single boron atom as ligand led us to report an
analyses of 5–7 indicate significant delocalization of the efficient route to s and agostic complexes that does not re-
electron density from the filled sB¢H orbital to the vacant quire the use of any preformed boron-containing ligands.[13b]
metal orbital. In an objective to design useful synthetic routes for these
types of complexes, we set out to test the possibility of differ-
ent transition metal precursors. In this regard, we found that
Complexes in which a s-bond acts as donor to a transition the metal chlorides [Cp*MCl2]2 (Cp* = pentamethylcyclopenta-
metal are recognized for dihydrogen, alkanes, silanes, and bor- dienyl, M = Ru, Rh, Ir) are very good precursors for the genera-
anes.[1–7] Over the past decades, s-borane complexes have tion of B-agostic and metallaboratrane complexes from borate
been of significant interest for both organic and inorganic ligands.[13d]
chemists due to the contributions in catalytic hydroboration, Design of polyfunctional ligands is one of the key challenges
dehydrogenation, and C¢H functionalization reactions.[5, 8–10] As to set definite properties in molecules. For example, the
a result, the chemistry of borane[4–8] and boryl[9, 10] has been pincer-type ligands with non-innocent character has led to stir-
studied actively, particularly for various early- and late-transi- ring success in the field of s-bond activation of small mole-
tion-metal complexes. For example, Hartwig and co-workers cules.[14] Therefore, we continue to search for new metal pre-
synthesized the most representative case of s-borane com- cursors containing the Cp*M fragment and suitable boron-con-
plexes of early transition metals, in which the B¢H bond of taining ligands. As a result, [Cp*Mo(CO)3Me] (1) and phenyl-
a neutral borane coordinated to the transition-metal center.[4] chalcogenoborates were found competent precursors for the
Weller reported a novel bis(s)aminoborane complex of rhodi- synthesis of s-borane/borate complexes. Treatment of
um by the displacement of a labile fluoroarene ligand from Li[BH3(SPh)] with 1 in toluene led to the isolation of a hydrobo-
[Rh(h6-C6H5F){P(C5H9)h2(2-C5H7)}][BArF4].[5] Based on the close re- rate complex [Cp*Mo(CO)2(m-H)BH2SPh] (2) in 31 % yield
(Scheme 1). This new compound was characterized by various
[a] R. Ramalakshmi, K. Saha, D. K. Roy, Prof. S. Ghosh
spectroscopic methods and single-crystal X-ray diffraction anal-
Department of Chemistry, Indian Institute of Technology Madras
Chennai 600 036 (India) ysis. In a similar fashion, reaction of the Se and Te analogues of
E-mail:
[email protected] [BH3SPh]¢ generated [Cp*Mo(CO)2(m-H)BH2EPh] (3: E = Se and
[b] Dr. B. Varghese 4: E = Te) in 23 and 15 % yields, respectively. The 11B{1H} NMR
SAIF, Indian Institute of Technology Madras spectra for 2 exhibits a sharp signal at d = ¢29.4 ppm that is
Chennai 600 036 (India)
shifted upfield relative to that observed for 3 (d = ¢27.1 ppm)
[c] Prof. A. K. Phukan
and 4 (d = ¢25.6 ppm). The 77Se NMR of 3 shows a peak at d =
Department of Chemical Sciences, Tezpur University
Tezpur 784 028 (India) ¢67.6 ppm and the 125Te NMR reveals a peak at d = 631 ppm.
Supporting information for this article is available on the WWW under The 1H NMR spectra of compounds 2–4 display upfield reso-
http://dx.doi.org/10.1002/chem.201503404. nances respectively at d = ¢8.27, ¢8.91, and ¢10.38 ppm,
Chem. Eur. J. 2015, 21, 17191 – 17195 17191 Ó 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Communication
tion positions on the Mo atom; thus, [Cp*Mo(CO)2(m-H)(EPh)]
(E = S, Se or Te) may be considered as a four-legged piano
stool.[15]
To gain some insight into the bonding of 2–4, we performed
density functional theory (DFT) calculations.[17] The natural-
bond-orbital (NBO) analysis shows that the charge transfer to
Scheme 1. Synthesis of hydroborate complexes 2–4.
both Mo and B increases in the order S < Se < Te. The lone pair
on the chalcogen atom is donated entirely, not only to the B
atom, but also to the Mo atom. This is verified by an increase
which are assigned to the Mo¢H¢B proton. In addition, the in the natural valence population of both B and Mo and a cor-
13
C NMR and the IR spectra of compounds 2–4 validate the responding decrease for the chalcogen atoms. Further, this has
presence of Cp* and CO ligands. been supported with the increase of computed natural charg-
The X-ray diffraction analysis was done at 293 and 173 K on es for Mo (qMo) and B (qB) and an increase in positive charge
orange crystals of 2 and 3 obtained from the slow evaporation for the chalcogen atoms in the order S < Se < Te (Table S1 in
of a hexane solution at 3 8C. The efforts to obtain X-ray quality the Supporting Information). The nature of chalcogen–boron
crystals of 4 failed. The solid-state X-ray structures, shown in interaction is probed by QTAIM (quantum theory of atom in
Figure 1, verifies the composition of 2 and 3 and reveals molecules) analysis on 2–4. Figure 2 shows the contour map of
Figure 2. Contour-line diagram of the Laplacian of the electron density in
the Mo-S-B plane of 2. Solid blue lines indicate charge depletion [r21(r) > 0]
and dashed maroon lines indicate charge concentration [r21(r) < 0]. Green
and red spheres denote bond critical points (bcp) and ring critical points
(rcp), respectively.
the Laplacian of the electron density r21(r) along the S¢B
Figure 1. Molecular structures and labeling diagram for 2 (top) and 3 bond of 2 exhibiting the polarization or diffuseness of the va-
(bottom). Selected bond lengths (æ) and angles (8) for 2: Mo1¢H1 1.80(4), lence-shell charge concentration (VSCC) zone of the sulphur
Mo1¢B1 2.576(7), Mo1¢S1 2.4880(14), B1¢S1 1.897(8); Mo1-B1-S1 65.5(2), S1- atom towards the boron atom, typical of donor–acceptor inter-
B1-H1 102(2), Mo1-S1-B1 70.5(2). For 3: Mo1¢H1A 1.98(16), Mo1¢B1
2.587(13), Mo1¢Se1 2.6070(12), B1¢Se1 2.017(14); Mo1-B1-Se1 67.7(4), Se1-
actions (Figure 2).[18] Similar topological features are also ob-
B1-H1A 107(9), Mo1-Se1-B1 66.6(4). tained for 3 and 4 (Figure S11 in the Supporting Information).
The chalcogen–boron interaction has more covalent character
in 2 than 3 and 4 as indicated by a higher value of electron
a unique {Mo-mH-B-E} (E = S or Se) metallaheterocycle. The density at the bond critical point (1b) and a more negative
Mo¢H distance of 1.80(4) æ in 2 can be compared with value for the energy density, H(r) at bcp (Table S2 in the Sup-
[CpMo(CO)2{P(BH3}(Ph){N[Si(CH3)3]2}], however, in 3 the Mo¢H porting Information).
distance (1.98(16) æ) is significantly longer than three standard Having isolated compounds 2–4 through hydroborate liga-
deviations of a range of Mo-H-Mo bridge distances 1.85– tion methodology and inspired by our earlier work on the syn-
1.89 æ. The Mo···B separation in 2 (2.577 æ) and 3 (2.587 æ) is thesis of various s-borate and agostic complexes of Ru with 2-
shorter than observed in mercaptobenzothiazole (mbtz),[13] we carried out the reaction
[CpMo(CO)2{P(BH3)(Ph){N(Si(CH3)3)2}}][15] (2.622(4) æ), however, of 1 with LiBH4 in presence of 2-mbtz (Scheme 2) that yielded
longer than the sum of the estimated covalent radii, 2.44– compound 5 in moderate yield along with release of elemental
2.49 æ. The Mo¢S (2.4880(14) æ) and Mo¢Se (2.6070(12) æ) sulfur. The 11B NMR of 5 shows a resonance at d = ¢20.6 ppm
distances in 2 and 3 are comparable with those of and the 1H NMR spectrum shows well-resolved signals for the
[(Cp*Mo)2B2H5(BER)2(m-h1-ER)] (E = S and Se).[16] The bridging hy- benzothiazole ligand and an upfield resonance at d =
drogens in compounds 2 and 3 occupy one of the coordina- ¢1.56 ppm with integral intensity of three hydrogens.
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Communication
Scheme 2. Synthesis of the N,S-carbene-anchored s-borate complex 5.
From the X-ray diffraction analysis, the identity of compound
5 was recognized as an N,S-carbene-supported s-borate com-
plex (Figure 3). The asymmetric unit of 5 contains two inde-
Figure 3. Molecular structure and labeling diagram for 5. Selected bond
lengths (æ) and angles (8): Mo2¢C30 2.155(7), Mo2¢H2 1.940(8), B2¢H2
1.41(8), B2¢N2 1.551(11), C30¢N2 1.311(8), C30¢S2 1.723(7); Mo2-C30-S2 Figure 4. Top) Contour-line diagram of the Laplacian of the electron density
135.0(3), Mo2-C30-N2 113.9(5), N2-B2-H2 113(3), C30-N2-B2 113.8(6). in the Mo-C-B plane of 5. Solid blue lines indicate charge depletion
[r21(r) > 0] and dashed maroon lines indicate charge concentration
[r21(r) < 0]. Green and red spheres denote bcp and rcp, respectively. Bot-
pendent molecules and the structural data presented here is tom) MOs responsible for the Mo sB¢H interaction.
!
from one of the units. The borane ligand in 5 binds to the mo-
lybdenum atom through a B-H-M, three-center, two-electron NBO based second-order-perturbation-energy analyses indicate
bond in an end-on fashion. The bridged B¢H bond distance significant delocalization of the electron density from the filled
(1.41(8) æ) is lengthened significantly relative to the terminal sB-H orbital to the vacant metal orbital resulting in a stabilizing
ones (1.11(2) æ), indicating that 5 can be classified as stretched interaction of 119.0 kcal mol¢1 (Figure 4 (bottom)).
s-complex. Another interesting feature of 5 is the presence of The precedence of structurally characterized agostic and
a N,S-carbene unit. The Mo¢C distance of 2.155(7) æ falls in the s-complexes of boron with early and late transition metals are
range observed for other metal N,S-HC complexes (listed in rare compared with hydrogen and silane complexes.[1a, 3a, 4a, 9]
Table S3 in the Supporting Information). Thus, in an effort to increase this library, we have carried out
The low-temperature 1H NMR spectrum of 5 exhibits distinct the reaction of the B-agostic [Cp*Ru(m-H)BHL2], (6; L = C7H4NS2)
signals for the metal-coordinated and terminal BH protons at with [Mn2 (CO)10] that led to the isolation of a transmetallation
d = ¢9.31 and 3.53 ppm in a 1:2 ratio. The variable-tempera- agostic complex [Mn(CO)3(m-H)BHL2], 7, in which the [Cp*Ru]
ture 1H NMR spectrum (Figure S9 in the Supporting Informa- unit has been replaced by isolobal and isoelectronic [Mn(CO)3]
tion) shows the existence of a fast scrambling between the co- unit (Scheme 3 and Figure 5).[19] The 11B NMR chemical shift of
ordinated and terminal BH protons. Further, based on the re- 7 shows a peak at d = ¢3.9 ppm; shifted down field compared
ported 13C NMR chemical shifts of transition-metal–N,S-hetero- with 6. The 1H NMR shows an upfield resonance at d =
cyclic carbene complexes, the signals at d = 213.8 ppm has ¢11.09 ppm for Mn-H-B along with chemical shifts for terminal
been assigned to the carbene carbon. B¢H and benzothiazole ligands. The Mn···B separation of
Although compound 5 has been defined as carbene/borate, 2.699 æ and the bond angle of Mn-H-B (136.88) in 7 are compa-
the QTAIM analysis effectively captures two key electronic fea- rable to [CpMn(CO)2(h1-BH3·L)] (L = NMe3 : Mn¢B = 2.682(3) æ,
tures, that is, interaction of the carbenic lone pair with Mo and Mn-H-B = 142(3)8; L = PMe3 : Mn¢B = 2.573(2) æ, Mn-H-B =
stabilization of the borane moiety through dative interaction 129(3)8).[6]
through the N end of the N,S-carbene molecule (Figure 4 Both NBO and AIM analyses predict similar electronic struc-
(top)). Thus, the bonding depiction of compound 5 is neither tures for 6 and 7. The calculated natural charge at the boron
carbene/borate nor aryl/borane; the scenario may be in be- and nitrogen (the one responsible for dative interaction with
tween these two illustrations (see Figure S13 in the Supporting boron) atoms, as well as Wiberg bond indices (WBI) of B¢N
Information for different resonance structures of 5). In addition, (0.64), B¢Hbridging (0.69) and M¢S (0.70 and 0.63; M = Ru, Mn)
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Communication
ratio of three. The IR stretching frequencies for B¢H and CO li-
gands are observed at 2436 and 1941 cm¢1, respectively. The
presence of the CO ligand is also confirmed by the 13C NMR
spectrum. Nevertheless, the identity of this new compound
was clear when a solid-state X-ray diffraction analysis was car-
ried out.
Based on the mass-spectrometry analysis in combination
with the solid-state X-ray structure, shown in Figure 6, com-
Scheme 3. Synthesis of the s-borane complexes 7 and 10.
Figure 6. Molecular structure and labeling diagram for 10. Selected bond
lengths (æ) and angles (8): C18¢N1 1.400(4), B1¢N1 1.576(5), B1¢Ru1
2.596(4), B1¢H1A 1.23(2), S1¢Ru1 2.3877(9), Ru1¢H1A 1.86(2); N1-C12-S1
126.1(3), N1-C12-S2 112.9(3), S1-C12-S2 121.0(2), C12-N1-C18 113.2(3), C12-
N1-B1 121.1(3), C18-N1-B1 125.2(3),C12-S1-Ru1 104.41(12), S1-Ru1-H1A
98.6(11).
pound 10 is formulated as [Cp*RuCO(m-H)BH2L] (L = C7H4S2N).
Figure 5. Molecular structure and labeling diagram for 7. Selected bond
As depicted in Figure 6 and Scheme 3, compound 10 can be
lengths (æ) and angles (8): B1¢N1 1.565(5), B1¢N2 1.546(5), B1¢H1A
1.182(17), Mn1¢H1A 1.71(2); N1-C1-S1 129.0(3), N1-C1-S2 112.4(3), S1-C1-S2 described as base-stabilized s-borane complex. The B¢N and
118.61(19), C8-S3-Mn1 100.60(11), S1-Mn1-S3 89.40(4). Ru¢B distances of 1.576(5) and 2.596(4) æ, respectively, length-
ened significantly compared with those of 9. The B1¢H1A
bond length (1.23(2) æ) is in the range observed for ruthenium
bonds, are similar for 6 and 7. Interestingly, the WBI values in- s-borane complexes, and comparable to that reported by
dicate a stronger Mn···B interaction in 7 (WBI = 0.227) than the Braunschweig for a vinyl(amino)borane chromium complex.[20]
corresponding Ru···B interaction in 6 (WBI = 0.168), which may The Ru-H-B bond angle of 113.18 is in agreement with other s-
partly explain the greater stability of 7 compared with 6 (the borane complexes of ruthenium.[7] With the observation that
calculated HOMO–LUMO gaps of 6 and 7 are 3.5 and 4.1 eV, re- [Mn2(CO)10] only acts as CO source, we performed the reaction
spectively). Further, the second-order-perturbation-energy of 9 with Group 6 monometalcarbonyl fragments and CO gas
analysis yield a value of 108.0 kcal mol¢1 for 7 compared with to yield 10 in maximum yield.
60.3 kcal mol¢1 for 6, resulting from the interaction between The molecular structure of 10, shown in Figure 6, clearly
the filled sB-H orbital with the vacant metal orbital of Mn and shows that upon addition of one CO ligand to the ruthenium
Ru, respectively. The topological parameters are remarkably center of 9, one of the Ru-H-B protons moves to the B¢H ter-
similar for 6 and 7 and the N!B interaction has a strong cova- minal. This was also established by a variable-temperature
1
lent character as exemplified by the higher value of the elec- H NMR study. The 1H chemical shift at d = ¢2.07 ppm col-
tron density and the negative value for the electronic energy lapsed at ¢10 8C, and on further cooling to ¢70 8C, two new
density at the bcp (1b = 0.142 a.u.; Hb = ¢0.106 a.u.; see signals appeared at d = ¢11.15 and 3.51 ppm in a 1:2 ratio
Table S2 in the Supporting Information). (Figure S10 in the Supporting Information). This evidently
Having in hand a bis(s)borate complex of ruthenium specifies a fast exchange between the Ru-H-B and B¢H pro-
[Cp*Ru(m-H)2BHL] (9), we performed the reaction of 9 with tons.
[Mn2(CO)10]. Although all our attempts to generate the trans- Geometry optimization of 10 yields similar structural fea-
metallation product [Mn(CO)3(m-H)2BHL] from 9 failed, the reac- tures as for 5 with respect to the interaction of the N,S-carbene
tion yielded a new compound (10) in 41 % yield (Scheme 3). with the borane unit. For example, all the B¢H and N¢B bond
The 11B NMR shows a peak at d = ¢21.7 ppm, shifted upfield lengths are similar in 5 and 10. In addition, the topological fea-
compared with 9 (d = 12.1 ppm). The 1H NMR shows the pres- tures and parameters of 5 and 10 are also similar (Figure S12
ence of one Cp* ligand at d = 1.8 ppm, which excludes the for- and Table S2 in the Supporting Information).
mation of any transmetallation product. The 1H NMR spectrum To sum up, this work describes a series of new agostic and
shows an upfield proton at d = ¢2.07 ppm with an intensity base-stabilized s-borane/borate complexes from different
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Communication
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