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Synthesis, Characterization, and Reactivity of Ruthenium Hydride Complexes

of N-Centered Triphosphine Ligands Andreas
Phanopoulos, Neil J. Brown, Andrew JP White, Nicholas J. Long,* and Philip W. Miller*
Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, UK

*S Supporting Information

ABSTRACT: The reactivity of the novel tridentate phosphine ligand N(CH2PCyp2)3 (N-triphosCyp, 2; Cyp = cyclopentyl) with various
ruthenium complexes was investigated and compared that of to the less sterically bulky and less electron donating phenyl derivative
N(CH2PPh2 )3 (N-triphosPh, 1). One of these complexes was subsequently investigated for reactivity toward levulinic acid, a potentially
important biorenewable feedstock. Reaction of ligands 1 and 2 with the precursors [Ru(COD)(methylallyl)2]
(COD = 1,5-cycloocatadiene) and [RuH2(PPh3)4] gave the tridentate coordination complexes [Ru(tmm){N(CH2PR2)3-ÿ3 P}]
(R = Ph (3), Cyp (4); tmm = trimethylenemethane) and [RuH2(PPh3){N(CH2PR2)3-ÿ3 P}] (R = Ph (5), Cyp (6)), respectively.
Ligands 1 and 2 displayed different reactivities with [Ru3(CO)12]. Ligand 1 gave the tridentate dicarbonyl complex [Ru(CO)2{N(CH2PPh2)3-
ÿ3 P}] (7), while 2 gave the bidentate, tricarbonyl [Ru(CO)3{N(CH2PCyp2)3-ÿ2 P }] (8). This was attributed to the greater electron-
donating characteristics of 2, requiring further stabilization on coordination to the electron-rich Ru(0) center by more CO ligands.
Complex 7 was activated via oxidation using AgOTf and O2, giving the Ru(II) complexes [Ru(CO)2(OTf){N(CH2PPh2)3-ÿ3 P}](OTf) (9)
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and [Ru(CO3) (CO){N(CH2PPh2)3-ÿ3 P}] (11), respectively. Hydrogenation of these complexes under hydrogen pressures of 3ÿ15 bar
gave the monohydride and dihydride complexes [RuH(CO)2{N- (CH2PPh2)3-ÿ3 P}] (10) and [RuH2(CO){N(CH2PPh2) 3-ÿ3 P}] (12),
respectively. Complex 12 was found to be unreactive toward levulinic acid (LA) unless activated by reaction with NH4PF6 in acetonitrile,
forming [RuH(CO)(MeCN){N- (CH2PPh2)3-ÿ3 P}](PF6) (13), which reacted cleanly with LA to form [Ru(CO){N(CH2PPh2)3-ÿ3 P}
{CH3CO(CH2)2CO2H- ÿ2 O}](PF6) (14). Complexes 3, 5, 7, 8, 11, and 12 were characterized by single-crystal X-ray crystallography.

ÿ INTRODUCTION phosphine or variance of the phosphine itself. Triphos-type ligands

have been shown to coordinate to a wide range of early and late
The vast body of academic literature and industrially applied
transition metals,17ÿ21 some of which have been evaluated for
ruthenium-catalyzed reactions1ÿ9 is testament to the versatility
catalytic activity. Early examples include Rh-triphosPh complexes
and importance of ruthenium-based catalysts. The types of Ru
used for hydrogenation and hydro-formylation of various alkenes22
catalytic transformations are diverse, varying from CÿC cross-
or the hydrogenation of quinoline, an important impurity found in
coupling reactions10 and activation of inert CÿH bonds11 to the
fossil fuels that requires degradation.23 More recently, Mo-
better-known metathesis12 and hydrogenation reactions.13 The
majority of these ruthenium catalysts incorporate either mono- or triphosPh complexes were shown to coordinate and activate N2,
ultimately for conversion to ammonia or other high-value nitrogen-
bidentate phosphine ligands, which are ubiquitous in homogeneous
catalysis owing to their highly tunable electronic and steric containing compounds,24 while Ru-triphos complexes have been
properties. Although less commonly used in catalytic applications employed in formic acid dehydrogenation25 and direct methylation
than mono- or bidentate analogues, tridentate phosphines offer of primary and secondary aromatic amines using carbon dioxide
well-defined coordination geometries that can affect the stability of and molecular hydrogen.26 Futhermore, Leitner et al . have
the catalytically active metal center, in some cases producing more reported the use of Ru-triphosPh systems in several highly
active and robust catalysts. desirable “green chemistry” reactions. A [Ru(acac)3]/triphos system
Consequently, tridentate ligands are receiving renewed academic was used for the stepwise and tunable hydrogenation of two
and industrial interest for both coordination biomass-derived carboxylic acids (levulinic and itaconic acid)
chemistry and catalysis.14ÿ16 ultimately to 2- and 3-methyltetrahydrofuran, respectively.
The most commonly studied tripodal phosphines are 1,1,1-
tris(diphenylphosphinomethyl)ethane (CH3C(CH2PPh2)3, tri-
phosPh) and its derivatives; these analogues mostly feature Received: January 8, 2014
changes to the arm length between the apical carbon and Published: March 26, 2014

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tively; in both cases greater activity and scope was demonstrated improve catalytic activity. Herein, we report a series of new
over the use of analogous mono- or bidentate phosphine ruthenium N-triphos complexes, including three with the novel
ligands.27 This is significant, as methyltetrahydrofur-an (MTHF) dicyclopentyl N-triphos ligand (N-triphosCyp, 2). The
has been promoted as a greener ethereal solvent due to its coordination chemistry of 2 is compared to that of the less bulky
production from renewable resources (such as corn starch), as phenyl derivative 1, using three different ruthenium precursors.
well as its relative immiscibility with aqueous in comparison to The reactivity of one of these complexes toward levulinic acid
tetrahydrofuran (THF), facilitating workup and recovery.28ÿ30 (LA) was assessed after initial activation by oxidation of the
A [Ru(COD)(methylallyl)2]/ triphos mixture solutions was used Ru(0) center, subsequent hydride formation under H2 pressure,
for the selective hydrogenolysis via CÿO bond cleavage of lignin and a final activation step involving reaction with a proton donor.
model compounds, a vital step in the valorization process that
aims to mildly depolymerize this natural product, while
maintaining the desired functionality.31 Finally, a preformed ÿ RESULTS AND DISCUSSION
ruthenium complex, [Ru(tmm){CH3C- ( CH2PPh2)3-ÿ3 P}] (tmm Ligand Synthesis. It has been previously shown by us that
= trimethylenemethane), was shown to give moderate turnover the coordination mode of N-triphos derivatives is controlled by
numbers for the hydrogenation of CO2 to methanol,32 a vital the steric constraints imposed by the phosphine arms;
step for the recycling of carbon that may eventually lead to the Consequently, the bulky di-tert-butyl and dicyclohexyl derivatives
realization of a sustainable carbon were found to exclusively form ÿ2 coordination complexes,
economy. resulting in one free pendant arm.17 The novel dicyclopentyl
Despite the great interest in triphos complexes, the synthesis derivative N-triphosCyp (2) was therefore selected, as its
of triphos ligands is not always simple. Typically, highly air and reduction in steric bulk from the previously studied derivatives
moisture sensitive metal phosphide reagents are required that should enable the desired tridentate coordination. A switch to
can result in low yields owing to incomplete substitution diarylphosphines were not explored, as dialkylphosphines
reactions. It would be desirable to obtain a more facile synthesis
possess the desired electron-donating ability required to
of triphos analogues that impart the same coordination chemistry adequately promote oxidative addition during catalytic cycles.
features and catalytic activity. The previously reported N- Ligand 1 was prepared as previously reported, via a
centered triphos ligand N,N,N-tris- (diphenylmethyl)amine, conveniently air-stable phosphonium salt intermediate (Scheme
where the central bridgehead CH3ÿ C moiety in triphosPh is 1a). Isolation and reaction of the phosphonium salt precursor
replaced by a single nitrogen atom to give N(CH2PPh2)3 (N- for ligand 2 was found to give reduced yields; Hence, ligand 2
triphosPh, 1), is conveniently synthe-sized via a phosphorus was prepared via a one-pot in situ method (Scheme 1b).
variation of the Mannich reaction from the corresponding
secondary phosphine.33 Despite this facile synthesis, complexes Scheme 1. Synthesis of (a) N-triphosPh via a Phosphonium
with N-triphos ligands remain rare with only, to the best of our Salt Intermediate and (b) N-triphosCyp via a
knowledge, a select few having been reported in the Dialkyl(hydroxymethyl)phosphine Intermediate
literature.17,33ÿ37 These ligands have previously been targeted
within our group, as their facial coordination simplifies
complexation by reducing the number of potential isomers, as
well as resulting in a cis conformation of any other coordinated
groups, facilitating reductive elimination during catalysis. It was
for these primary reasons that mer-coordinating analogues were
not investigated, despite many such ligands being studied for
both complexation and catalysis.38ÿ40 Examples of such
coordination geometries can be found in the vast body of work
by Milstein et al., who have studied many pincer-type complexes,
including the coordination and reactivity of PONOP ligands,41
as well as CNN-, PNN-, and PNP-type ligands for activity toward
hydrogenation of straight and cyclic esters,42,43 and coupling
reactions to form imines and pyrroles.44,45 Other examples
include POP- and PSP-type ligands that have similarly been
investigated.46,47 Our previous investigations of N-triphosCyp was prepared in moderate yield (59%) via the
N-triphos ligands have shown that steric encumberment of reaction of ammonia and in situ generated dicyclopentyl-
the phosphine arms determines whether a ÿ3 or ÿ2 coordination (hydroxymethyl)phosphine. Cooling the reaction mixture to ÿ35
geometry is achieved.17 Bulky phosphino-alkyl groups °C overnight resulted in the formation of a white crystalline solid
(dicyclohexyl- or di-tert-butylphos-phine) only coordinate that was isolated in high purity simply by filtration. The 31P{1 H}
through two arms, while the third remains pendant; In addition, NMR spectrum showed a single resonance at ÿ ÿ18.4, and
Gade et al. have recently shown that the smaller isopropyl subsequent NMR spectra analysis revealed it does not exhibit
derivative can bind through all three arms.36 Since triphos strong J coupling between phosphorus and other spin-active
complexes have previously been demonstrated to be highly nuclei. The reason for these unknown, however similar, spectral
effective catalysts, it would be of significant interest to expand characteristics were observed for the ethyl, isopropyl, tert-butyl,
the family of known ÿ3 - coordinating triphosphine ligands. and cyclohexyl derivatives, suggesting that this can be
Investigation into a wider range of sterically larger or smaller considered characteristic of this kind of ligand.17,37,48
phosphines, in addition to exploring various phosphine
substituents in order to tune electronic properties, may help Comparison of Coordination Chemistry between N-triphosPh
elucidate critical aspects to and N-triphosCyp. Recent papers by the groups of

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Scheme 2. Summary of N-triphosPh and N-triphosCyp Ru Complexes Prepared during This Study

Leitner and Gade have shown [Ru(COD)(methylallyl)2] to be

a versatile starting material for producing ÿ3 triphosphine
ruthenium complexes.31,36,37 When ligands 1 and 2 were
reacted with 1 equiv of [Ru(COD)( methylallyl)2] in toluene
under reflux, all three phosphine arms were found to
coordinate to the Ru center, displacing the COD ligand and
one methylallyl moiety, generating facially capping ÿ3
complexes (Scheme 2). Thus, ligands 1 and 2 afford the
complexes [Ru(tmm){N(CH2PPh2)3-ÿ3 P}] (3) and [Ru(tmm)
{N- (CH2PPh2)3-ÿ3 P}] (4), respectively. The symmetric
nature of complexes 3 and 4 is evident from the 31P{1 H}
NMR spectra, which each display singlets at ÿ 18.2 and 14.2, respectively.
Similar to the compound [Ru(tmm){N(CH2Pi Pr2)3-ÿ3 P}]
reported by Gade et al.,36 a singlet is observed for the signals
assigned to the methylene protons of the tmm moieties in
complex 4, while the quaternary carbon (13C{1 H} ÿ 102.8) is
Figure 1. Crystal structure of the C3-symmetric complex 3 (50%
highly shifted, indicating ÿ4 coordination. Characterization of
probability ellipsoids). Selected bond lengths (Å) and angles (deg)
complex 3 by NMR proved difficult due to solubility issues, for 3: Ru(1)ÿP(3), 2.2828(3); Ru(1)ÿC(21), 2.085(2); Ru(1)ÿC(22),
allowing only a weak 31P{1 H} NMR spectrum to be recorded. 2.2518(13); P(3)ÿRu(1)ÿC(21), 125.820(8); P(3)ÿRu(1)ÿC(22),
High-resolution mass spectrometry (HRMS) showed only one 103.89(4); P(3)ÿRu(1)ÿP(3A), 89.211(12); P(3)ÿRu(1)ÿC(22A),
peak cluster displaying the expected isotope pattern for 164.01(4); P(3)ÿRu(1)ÿP(3B), 89.211(12); P(3)ÿRuÿC(22B),
ruthenium, strongly suggesting a monometallic structure. 99.93(4); C(21)ÿRu(1)ÿC(22), 38.51(4); C(21)ÿRu(1)ÿP(3A),
Additionally, crystals of 3 suitable for X-ray diffraction analysis 125.820(8); C(21)ÿRu(1)ÿC(22A), 38.51(4); C(21)ÿRu(1)ÿP- (3B),
were grown by allowing a dilute toluene solution to stand at 125.820(8); C(21)ÿRu(1)ÿC(22B), 38.51(4); C(22)ÿRuÿ P(3A),
room temperature for 5 days (Figure 1). The molecular 99.93(4); C(22)ÿRu(1)ÿC(22A), 65.26(6); C(22)ÿRu(1)ÿ P(3B),
164.01(4); C(22)ÿRu(1)ÿC(22B), 65.26(6); P(3A)ÿRu(1)ÿ P(3B),
structure revealed the complex has crystallographic C3
89.211(12); P(3A)ÿRu(1)ÿC(22A), 103.89(4); P(3A)ÿRu(1)ÿC(22B),
symmetry about an axis that passes through N(1) and the 164.01(4); P(3B)ÿRu(1)ÿC(22A), 99.93(4); P- (3B)ÿRu(1)ÿC(22B),
ruthenium center, as well as confirming the expected distorted- 103.89(4); C(22A)ÿRu(1)ÿC(22B), 65.26(6).
octahedral structure. The short RuÿCtmm distance observed
(2.085 Å) also supports an ÿ4 coordination mode. Unlike
complex 3, the cyclopentyl derivative complex 4 is remarkably
soluble in many solvents, and it is due to this, as well as its 2). Both complexes show a characteristic 31P{1 H} NMR
air and moisture sensitivity, that it was only possible to be AM2X splitting pattern, manifesting as two doublets of triplets
isolated in relatively low yields (20%). Attempts to further and an apparent triplet. The two phosphine arms of the NP3
extract or precipitate the desired complex invariably resulted ligands trans to the hydrides are easily identified from the
in decomposition to “ruthenium black” and free ligand. relative 2:1 intensity in comparison to the other signals. The
Reaction of ligands 1 and 2 in toluene at 50 °C with remaining two phosphorus signals were assigned on the basis
[Ru(H)2(PPh3)4] results in ligand substitution of three PPh3 of 2D 1 H/31P{1 H} and 13C{1 H}/31P{1 H} NMR correlation
units, resulting in the tridentate complexes [RuH2(PPh3){N- experiments, indicating the remaining arms on the NP3
(CH2PR2)3-ÿ3 P}] (R = phenyl (5), cyclopentyl (6)) (Scheme ligands have ÿP values of 26.9 and 25.6 for complexes 5 and 6, respectively.

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The 1H NMR spectra show distinctive hydride resonances

that appear as complex multiplets centered around ÿ ÿ7.73
H{31P} ÿ9.72 for complexes 5 and 6, respectively. and 1
When spectra were recorded, these signals were found to
simplify to singlets (Figure S7, Supporting Information).
Crystals of 5 suitable for X-ray diffraction analysis were
grown from a concentrated ether solution, and the structure
shows a distorted-octahedral coordination geometry (Figure 2). Start-

Figure 3. Crystal structure of 7 (50% probability ellipsoids). Selected

bond lengths (Å) and angles (deg) for 7: RuÿP(3), 2.3460(4); Ruÿ
P(5), 2.3515(4); RuÿP(7), 2.3601(4); RuÿC(50), 1.8839(17); Ruÿ
C(60), 1.8950(15); P(3)ÿRuÿP(5), 93.667(13); P(3)ÿRuÿP(7),
86.450(13); P(3)ÿRuÿC(50), 147.51(5); P(3)ÿRuÿC(60), 87.27(5);
P(5)ÿRuÿP(7), 86.265(13); P(5)ÿRuÿC(50), 118.55(5); P(5)ÿRuÿC(60),
109.37(5); P(7)ÿRuÿC(50), 91.27(5); P(7)ÿRuÿ C(60), 163.49(5);
C(50)ÿRuÿC(60), 85.88(7).

Unlike [Ru(COD)(methylallyl)2] and [RuH2(PPh3)4], for

which ligands 1 and 2 showed identical reactivity, reaction of
3 equiv of ligand 2 with [Ru3(CO)12] in toluene under reflux
Figure 2. Crystal structure of 5 (50% probability ellipsoids). Selected overnight did not lead to tridentate coordination; instead, the
bond lengths (Å) and angles (deg) for 5: RuÿP(3), 2.2696(5); Ruÿ ÿ2 complex [Ru(CO)3{N(CH2PCyp2)3-ÿ2 P}] (8) was formed.
P(5), 2.3311(6); RuÿP(7), 2.3358(6); RuÿP(50), 2.3197(5); Crystals suitable for X-ray diffraction analysis were grown by
P(3)ÿRuÿP(5), 95.54(2); P(3)ÿRuÿP(7), 88.06(2); P(3)ÿRuÿP(50), layering a CH2Cl2 solution of 8 with methanol, confirming
149.45(2); P(5)ÿRuÿP(7), 86.37(2); P(5)ÿRuÿP(50), 107.80(2); the bidentate coordination of 2, which coordinates in a
P(7)ÿRuÿP(50), 112.31(2). distorted-trigonal-bipyramidal geometry (Figure 4 and Table 1). The

tially, synthesis of complex 5 was performed under reflux in

diglyme; However, the inherent instability of the precursor
[RuH2(PPh3)4] under these reaction conditions resulted in
significantly lower yields. These lower yields were presumably
due to a significant amount of decomposition occurring in
tandem with product formation, as the precursor is highly
fluxional in solution due to the disassociation/association of
PPh3. Changing the solvent to toluene and gently heating to
50 °C resulted in a yield increase from 19% to 54%.
[Ru(CO)2{N(CH2PPh2)3-ÿ3 P}] (7), previously reported by
us but not structurally characterized,48 can be formed in high
yields via the reaction of 3 equiv s of 1 with [Ru3( CO)12] in
toluene under reflux. The 31P{1 H} NMR spectrum of 7
shows a single phosphorus resonance at ÿ 8.95 that remains
unaltered when the temperature is lowered to ÿ50 °C,
demonstrating the highly fluxional nature of the complex in
solution. X-ray diffraction analysis of crystals grown from a
concentrated toluene solution show that, when crystalline,
this complex adopts a distorted-square-pyramidal structure Figure 4. Structure of one (8-A) of the eight independent complexes
(for the square-based-pyramidal parameter ÿ of 7 see Table present in the crystals of 8 (50% probability ellipsoids).
S2 in the Supporting Information) ( Figure 3). Complex 7 is
valuable as a precursor complex, from which a wide variety
of potentially catalytically interesting complexes can be crystals of 8 were found to contain eight crystallographically
synthesized. It can be prepared in high yield and is a robust independent complexes (8-Aÿ8-H). Unsurprisingly, the
and stable complex that can be handled in air in the solid N(1)···Ru separation seen in 8 is much larger (by ca. 0.46 Å)
state, proving to be stable for days and only slowly oxidizing than those seen in the complexes with a tridentate N-triphos
after several weeks to the carbonate complex [Ru(CO3) (CO) {N(CH2PPh2)3-ÿ3 P}] (11).
ligand (Table S3, Supporting Information). Neither sustained
This transformation can be prevented by storing complex 7 further heating to 165 °C in diglyme nor irradiation with a 400
under nitrogen. W UV light resulted in ejection of a CO ligand and subsequent
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Table 1. Selected Bond Lengths (Å) for the Eight Independent Complexes (AÿH) Present in the Crystals of 8
Ru(1)ÿP(3) Ru(1)ÿP(5) Ru(1)ÿC(38) Ru(1)ÿC(39) Ru(1)ÿC(40)
TO 2.3861(14) 2.3710(15) 1.902(6) 1.918(6) 1904(6)
b 2.3669(14) 2.3778(15) 1.881(7) 1.899(6) 1908(7)
c 2.3785(14) 2.3732(13) 1.895(6) 1.915(6) 1,894(6)
d 2.3800(14) 2.3837(14) 1.898(7) 1.907(7) 1,874(7)
AND
2.3685(16) 2.3846(15) 1.895(6) 1.900(8) 1904(8)
F 2.3672(14) 2.3866(14) 1.881(6) 1.907(7) 1,895(7)
g 2.3937(14) 2.3806(14) 1.904(6) 1.895(6) 1915(7)
h 2.3591(14) 2.3845(14) 1.908(6) 1.912(6) 1902(6)

Scheme 3. Activation of Complex 7 by Oxidation using Two Different Oxidants

chelation of the pendant arm. Heating only resulted in while the other is noncoordinating. This is also inferred from
decomposition of the complex into uncharacterizable products. the FT-IR spectrum of 9, which shows several very broad and
Complex 8 remained completely unreactive under UV intense peaks in the region 1158ÿ1279 cmÿ1 , suggesting two
irradiation, with only starting material being observed, even different triflate environments. The presence of two carbonyl
after several hours, suggesting that the carbonyl ligands are ligands is also evident from the FT-IR spectrum as two peaks at
highly stabilizing for the electron-rich ruthenium center. The 2055 and 2095 cmÿ1 .
increased electron-donating ability of the dicyclopentylphos- Reaction of 9 with molecular hydrogen at 3 bar for 18 h at 70
phine arms (cf. diphenylphosphine) must require the °C in THF led to high-yielding formation of the monohydride
ruthenium to be further stabilized by additional carbonyl species [RuH(CO)2{N(CH2PPh2)3-ÿ3 P}](OTf) (10) along
ligands in comparison to the corresponding ÿ3 N-triphosPh with concomitant formation of 1 equiv of triflic acid. The 31P{1 H}
complex 7. NMR spectrum of 10 still displays a doublet and triplet
Synthesis of Ruthenium Hydride Complexes from similar to those seen for complex 9, while the 19F{1 H} NMR
[Ru(CO)2{N(CH2PPh2)3-ÿ3 P}] (7) and Subsequent Reac- tivity. spectrum, as expected, displays one resonance corresponding to
1
In comparison to [Ru(CO)2(PPh3)3], which forms the the noncoordinating triflate anion. The H NMR spectrum of
dihydride complex [RuH2(CO)2(PPh3)2] at room temperature 10 shows a characteristic doublet of triplets hydride signal
under 1 bar of H2, 49 complex 7 is unreactive toward molecular centered at ÿ ÿ6.75.
hydrogen even under forcing conditions of 50 bar and 100 °C. Oxidation of 7 using molecular oxygen (Scheme 3), by
This is due to the added stability of the chelating NP3 tridentate deliberate exposure of a solid sample to air for several weeks or
ligand and the reduced Ru(0) center, which is further stabilized by bubbling O2 through a toluene solution of 7 for ca. 20 min,
by electron-withdrawing CO ligands. In order to produce a resulted in conversion to the carbonate complex [Ru(CO3)-
more reactive 16-electron complex, oxidation of 7 was (CO){N(CH2PPh2)3-ÿ3 P}] (11). Reactivity similar to this has
undertaken using two different oxidizing agents (Scheme 3). been observed for another ruthenium triphosphine complex
Reaction of 7 with 2 equiv of AgOTf in CH2Cl2 at room using the mer-coordinating triphosphine PhP-
fifty
temperature resulted in instant precipitation of metallic silver (CH2CH2CH2PCy2)2. The presence of the new carbonate
and the formation of [Ru(CO)2(OTf){N(CH2PPh2)3-ÿ3 P}]- ligand can clearly be observed in the FT-IR spectrum of 11,
(OTf) (9). The slow diffusion of diethyl ether into the CH2Cl2 which now displays only a single CO stretch at 1994 cmÿ1 and
solution gave a yellow crystalline precipitate that displayed a additional stretches typical of bidentate carbonate at 1565,
sharp doublet and triplet in the 31P{1 H} NMR spectrum at ÿ 1434, 1272, and 1092 cmÿ1 . 51 Crystals suitable for X-ray
ÿ23.9 (2P) and 19.6 (1P), respectively. This implies diffraction analysis of complex 11 were grown by layering a
tridentate coordination of 1 persists; However, the complex is concentrated CH2Cl2 solution with toluene and allowing this
now six-coordinate with two different ancillary ligands. The mixture to stand at room temperature overnight (Figure 5),
presence of two distinct singlets in the 19F{1 H} NMR spectrum confirming the bidentate coordination mode of carbonate.
at ÿ ÿ76.8 and ÿ78.5 indicates that one triflate is coordinating Similar to the crystal structures of 3 and 5, 11 was found to

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Figure 6. Crystal structure of 12 (50% probability ellipsoids).

Selected bond lengths (Å) and angles (deg) for 12: RuÿP(3),
2.3337(6); Ruÿ P(5), 2.3359(6); RuÿP(7), 2.3532(6); RuÿC(50),
Figure 5. Structure of one (11-A) of the two independent complexes 1.881(3); P(3)ÿRuÿP(5), 88.95(2); P(3)ÿRuÿP(7), 90.48(2);
present in the crystals of 11 (50% probability ellipsoids). P(3)ÿRuÿC(50), 99.99(8); P(5)ÿRuÿP(7), 88.36(2); P(5)ÿRuÿC(50),
99.47(8); P(7)ÿRuÿC(50), 166.97(8).

adopt a distorted-octahedral geometry and crystallized as two

crystallographically independent complexes (11-A and 11-B)
(Table 2). hydrogenation reactions, as the dihydride complex 12 would
Reaction of 11 with a modest pressure of molecular form readily in situ before undergoing any necessary activation
hydrogen (3 bar) led to the formation of the neutral dihydride steps prior to catalysis.
species [Ru(H)2(CO){N(CH2PPh2)3-ÿ3 P}] (12) within 18 h, Attempts to activate 8 by oxidation and facilitate tandem ÿ3
although higher pressures (ÿ15 bar) gave complete conversion coordination were not successful. Oxidation using O2 did not
within 2 h; layering a concentrated toluene solution with give the analogous carbonate complex observed with 11 but
methanol gave crystals suitable for X-ray diffraction analysis instead led to decomposition and oxidation of the ligand.
(Figure 6). Complex 12 shows an apparent doublet of doublets Presumably the pendant third arm reduces the overall stability
1H NMR
splitting pattern for the hydride resonance in the of 8, making it more susceptible to oxidative degradation
spectrum, centered around ÿ ÿ6.50, instead of the expected processes.
doublet of triplets due to phosphorus coupling. This same The transformation of biomass-derived products into platform
pattern was reported by Leitner et al. for the analogous chemicals and solvents is of significant industrial interest, as
TriphosPh complex [RuH2(CO){CH3C(CH2PPh2)3-ÿ3 P}].52 these can offer green alternatives to products previously only
Complex 12 is reactive toward chlorinated solvents, instantly accessible via petrochemical routes. The triphos complex
reacting with CHCl3 and more slowly with CH2Cl2, forming [RuH2(CO){CH3C(CH2PPh2)3-ÿ3 P}] has previously been
three separate uncharacterized products, as is evident from reported as an active catalyst for the hydrogenation of biomass-
2D-31P{1 H} NMR correlation experiments. The previously derived acids, such as levulinic acid (LA), to industrial
mentioned TriphosPh analogue has been implicated in several solvents.27, 52 The reactivity of the equivalent N-triphos
important catalytic cycles as a dormant form of the active complex 12 with LA was found to be markedly different from
catalytic species, hypothesized to be the cationic monohydride that of [RuH2(CO){CH3C(CH2PPh2)3-ÿ3 P}]. When 1 equiv of
52
[RuH{CH3C(CH2PPh2)3-ÿ3 P}]+ , including the hydrogena- LA was treated with 12, no reaction was found to occur in
tion of the biomass-derived levulinic and itaconic acids, as well either nonpolar (C6D6) or polar (THF) solvents, even after
as CO2 reduction to methanol using hydrogen.27,32 heating under reflux overnight. In contrast, [RuH2(CO)-
The use of the air-stable carbonate complex 11 as a {CH3C(CH2PPh2)3-ÿ3 P}] was reported to react cleanly with
precursor for the synthesis of 12 and its analogues offers a LA to form the coordinated complex [RuH{CH3C- (CH2PPh2)3-
route that is easier and milder than those previously reported ÿ3 P}{CH3CO(CH2) 2CO2H-ÿ2 O}], with concom-itant release
for the equivalent Triphos-Ru dihydride complexes. These of H2 and CO.52 The lower reactivity of 12 toward LA can be
previous synthetic schemes require either harsh reaction overcome by initial in situ activation through formation of a
conditions (120 bar of H2, 150 °C, 20 h)52 or several highly monohydride cationic species by reaction with the proton
air-sensitive steps.53,54 Since 11 is readily converted to 12 donor NH4PF6, which has previously been shown to react
under pressures of hydrogen, 11 may be used as a stable precatalystwith
for dihydride ruthenium complexes in this fashion.55

Table 2. Selected Bond Lengths (Å) for the Two Independent Complexes (A and B) Present in the Crystals of 11

AB TO b

Ru(1)ÿP(3) 2.4018(7) 2.4188(7) Ru(1)ÿO(51) 2.1303(19) 2.1265(19)

Ru(1)ÿP(5) 2.2985(7) 2.2872(8) Ru(1)ÿO(52) 2.132(2) 2.124(2)
Ru(1)ÿP(7) 2.3007(7) 2.2986(7) Ru(1)ÿC(60) 1.906(3) 1.905(3)
Ru(1)ÿC(50) 2.537(3) 2.537(3)

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Scheme 4. Reaction of 12 with NH4PF6 To Form 13 and Subsequent Coordination of Levulinic Acid To Form 14

When 12 is reacted at room temperature with NH4PF6 in a

coordinating solvent such as acetonitrile, it undergoes initial
hydride loss as H2, forming the reactive cationic 16-electron
species [RuH(CO){N(CH2PPh2)3-ÿ3 P}]+ that rapidly stabilizes
through coordination of acetonitrile, forming [RuH(CO)- (MeCN)
{N(CH2PPh2)3-ÿ3 P}](PF6) (13) (Scheme 4). This intermediate
species is highly reactive and gives a 31P{1 H}
NMR spectrum that shows a multiplet and two doublets of doublets at ÿ ÿ12.4, 3.9 (2 JPP =
2
31.6 Hz, JPP = 27.9) and 26.5 (2 JPP = 32.4 Hz, JPP = 22.3), respectively. The characteristic
2
pseudo doublet of doublets in the hydride region of the H NMR spectrum of 12 has now been
1
replaced by a pseudo doublet of triplets for 13 at ÿ ÿ6.3 (2 JHP = 77.5 Hz, JHP = 16.4 Hz).

The addition of 1.5 equiv of LA to a solution of 13 resulted in

LA coordination to ruthenium through two oxygen donors via
initial loss of hydride (as H2) and the bound MeCN, forming
[Ru(CO){N(CH2PPh2)3-ÿ3 P}{CH3CO(CH2)2CO2H- ÿ2 O}]
1
(PF6) (14) (Scheme 4). H and 31P{1 H} NMR spectra
were recorded hourly for the reaction between 13 and LA at
room temperature. The proton spectra showed the gradual
disappearance of the RuÿH signal (Figure 7), while the
phosphorus signals of 13 in the 31P{1 H} NMR spectra also
disappear and are replaced by a new pseudo triplet and doublet
of 14 at ÿ ÿ 16.2 (2 JPP = 26.4 Hz) and 19.8 (2 JPP = 26.4 Hz),
respectively (Figure 8). The apparent chemical equivalence of
two phosphorus atoms arises from the similarity of the two
coordinating oxygen atoms of LA trans to these phosphorus
atoms, resulting in the observed apparent triplet and doublet
instead of the expected three doublets of doublets signals. Figure 7. Stacked 1H NMR spectra showing the hydride region for the
Continued NMR analysis revealed that the reaction is complete conversion of 13 to 14.
after 21 h.
The remarkable difference in reactivity between 12 and 13
with LA has implications for the use of these complexes as
hydrogenation catalysts: namely, that 12 will not be an active Complex 7 was activated via oxidation using either AgOTf or
catalyst for the hydrogenation of LA since the two components oxygen, resulting in the formation of [Ru(CO)2(OTf){N-
do not interact, presumably due to the high stability of 12. (CH2PPh2)3-ÿ3 P}](OTf) (9) and [Ru(CO3) (CO){N- (CH2PPh2)3-
Consequently, a proton source is necessary for the preactivation ÿ3 P}] (11). Subsequent hydrogenation of these complexes
of this complex before LA can bind and subsequently undergo
resulted in the facile formation of the ruthenium hydride
catalytic hydrogenation.
complexes [RuH(CO)2{N(CH2PPh2)3-ÿ3 P}](OTf) (10) and
[RuH2(CO){N(CH2PPh2)3 -ÿ3 P}] (12). The reac-tivity of 12
ÿ CONCLUSIONS
toward levulinic acid was investigated and found to coordinate
The coordination chemistry of the novel ligand N(CH2PCyp2)3 only after an additional activation step with the proton donor
(N-triphosCyp) was compared to that of the known N- NH4PF6 to give the solvent-bound [RuH(CO)- (MeCN)
(CH2PPh2)3 (N-triphosPh) using three different ruthenium {N(CH2PPh2)3-ÿ3 P }](PF6) (13). This intermediary complex
precursors. In two instances the analogous facially capping
was found to react cleanly with levulinic acid via loss of hydride
tridentate complexes were formed (complexes 3ÿ6). Reaction
(as H2) and acetonitrile. Levulinic acid then coordinates in a
of ligands 1 and 2 with [Ru3(CO)12] resulted in a less bulky
phenyl derivative, forming the tridentate dicarbonyl species bidentate fashion through two oxygen donors, affording the
[Ru(CO)2{N(CH2PPh2)3-ÿ3 P}] (7), while the more bulky cationic complex [Ru(CO){N(CH2PPh2)3-ÿ3 P}-
cyclopentyl derivative exclusively gave the bidentate tricarbonyl {CH3CO(CH2)2CO2H-ÿ2 O}](PF6) (14) . Catalytic testing of
species [Ru(CO)3{N(CH2PCyp2)3-ÿ2 P}] (8). complexes 3ÿ12 is currently underway.

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Figure 8. Stacked 31P{1 H} NMR spectra showing the conversion of 13 to 14.

2
ÿ EXPERIMENTAL SECTION Cyp), 13C{1 H} NMR (CDCl3, 101 MHz): ÿ JCP = 9.6 Hz, CH2
26.0 (d, 27.6 (s, CH2 Cyp), 27.8 (d, JCP = 40.8 Hz, CHCyp),151.2 (d ,
1
General Considerations. All preparations were carried out using
JCP = 54.0 Hz, PCH2OH). 31P{1 H} NMR (CDCl3, 162 MHz): ÿ 31.8
standard Schlenk line techniques under an inert atmosphere of N2
(s). HRMS (ESI): m/z calcd for C12H24O2P ([M ÿ Cl]+ ) 231.1513,
unless otherwise stated. Solvents were dried over standard drying
found 231.1509. Anal. Calcd for C12H24O2PCl (found): C, 54.03
agents and stored over 3 Å molecular sieves. All starting materials were (54.16); H, 9.07 (8.94).
of reagent grade purchased from either Sigma-Aldrich Chemical Co. or N,N,N-Tris((dicyclopentylphosphino)methyl)amine (N-tri- phosCyp,
VWR International and used without further purification. Ligand 1 was 2). Method A. In a Schlenk flask were placed dicyclopentylphosphine
prepared as previously reported.33,48 1 H, 13C{1 H}, and 31P{1 H} (1.00 g, 5.87 mmol) and methanol (5 mL).
NMR spectra were recorded on Bruker AV-400, AV-500, and DRX-400 Degassed aqueous formaldehyde solution (35 wt %, 0.60 mL) was
spectrometers at 294 K unless otherwise stated. Chemical shifts are added, and the solution was stirred for 3 h at room temperature. A
reported in ppm using the residual proton impurities in the solvents. methanolic solution of NH3 (2 M, 0.98 mL) was then added and the
Pseudo triplets and pseudo doublets of triplets that occur as a result of solution brought to reflux for 4 h, forming an opaque emulsion. The
identical J value coupling to two or more chemically nonequivalent solution was placed in a freezer overnight, which resulted in the
nuclei are assigned as dd, dt, or ddd and are recognized by the inclusion formation of a white crystalline precipitate (651 mg, 1.15 mmol, 59%).
of only one or two J values. 13C NMR spectra were assigned with the 1
H NMR (C6D6, 400 MHz): ÿ 1.42ÿ2.09 (m, 54H, Cyp), 3.19 (s, 6H,
aid of DEPT-135, HSQC, and HMBC correlation experiments. Mass NCH2P). 13C{1 H} NMR (C6D6, 101 MHz): ÿ 26.5 (d, 2
JCP = 6.9
spectrometry analyzes were conducted by the Mass Spectrometry 2
CH2 Cyp), 26.8 (d, JCP = 7.0 Hz, CH2 Cyp), 30.9 (d, 3Hz, JCP = 1.8
Service, Imperial College London. Infrared spectra were recorded on a CH2 Cyp), 31.0 (br s, CH2 Cyp ), 36.1 (d,1Hz, JCP = 12.5 Hz, CHCyp),
Perkin-Elmer Spectrum 100 FT-IR spectrometer. 58.4 (m, NCH2P ). 31P{1 H} NMR (C6D6, 162 MHz): ÿ ÿ18.5 (s). HRMS
Elemental analyzes were carried out by Mr. Stephen Boyer of the (ES): m/z calcd for C33H60NP3O3 ([M + HO3] + ) 612.3864, found
Department of Health and Human Science, London Metropolitan 612.3871. Anal. Calcd for C33H60NP3 (found): C, 70.30 (70.25); H,
University. X-ray diffraction analysis was carried out by Dr. Andrew 10.73 (10.67); N, 2.49 (2.54).
White of the Department of Chemistry at Imperial College. Details of the Method B. In a Schlenk flask were placed dicyclopentyl-
single-crystal X-ray diffraction analysis can be found in the Supporting (hydroxymethyl)phosphonium chloride (626 mg, 2.35 mmol), NEt3 (0.76
Information. mL), and methanol (10 mL), and the solution was stirred for 10 min at
Dicyclopentyl(hydroxymethyl)phosphonium Chloride. In a Schlenk room temperature. Subsequent addition of NH3 (2 M, 0.39 mL) to the
flask were placed dicyclopentylphosphine (1.00 g, 5.87 mmol), degassed solution and stirring under reflux for 2 h resulted in an opaque emulsion,
aqueous formaldehyde solution (35 wt%, 1.10 mL), and degassed which when left in the freezer overnight allowed precipitation of the
concentrated HCl (37 wt%, 0.53 mL). The solution was stirred for 20 product as a white powder. The powder was washed with methanol (3
min at room temperature. Solvent was removed to give a viscous gum × 2 mL) and dried in vacuo to affordably pure 2 with characterization
that was subsequently crystallized from acetone after being cooled to data identical with those produced via method A (98.9 mg, 0.175 mmol,
ÿ5 °C to initiate crystallization. A white crystalline solid was obtained 45%).
that was filtered while cold, washed with diethyl ether (3 × 2 mL), and [Ru(tmm){N(CH2PPh2)3-ÿ3 P}] (3). To a solution of 1 (357 mg, 0.584
1H
dried in vacuo (683 mg, 2.56 mmol, 44%). mmol) in toluene (5 mL) was added [Ru(COD)(methylallyl)2] (187 mg,
NMR (CDCl3, 400 MHz): ÿ 1.60ÿ2.20 (m, 16H, CH2 Cyp), 2.49ÿ2.62 0.585 mmol), and the solution was stirred under reflux for 90 h. Within
(m, 2H, CHCyp), 4.62 (s, 4H, PCH2OH), 5.21 (br s, 2H, OH ). minutes the colorless solution turned yellow and

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Inorganic Chemistry Article

2 2
effervescence was observed. The product was observed to precipitate during 2P, Pcis), 25.6 (dt, JPPh3 = 212.4 Hz, JPP = 28.2 Hz, 1P, Ptrans), 61.9 (dt,
the course of the reaction as an off-white powder that was highly insoluble in 2
JPPh3P = 213.2 Hz,
2
JPPh3P = 22.9 Hz, 1P, PPh3). FT-IR (ÿ/cmÿ1 ): hydride
many solvents, hindering characterization and prohibiting collection of a 13C{1
stretches 1881, 1850. HRMS (ES): m/z found 394.1654 (85%), 751.2789 (60%).
H} NMR spectrum. The precipitate was isolated via cannula filter, washed with
Anal. Calcd for C51H77NP4Ru (found): C, 65.92 (65.84); H, 8.35 (8.40); N,
toluene (3 × 3 mL), and dried in vacuo (259 mg, 0.338 mmol, 58%). Crystals
1.51 (1.60).
suitable for X-ray diffraction analysis were grown from a dilute toluene solution
Synthesis of [Ru(CO)2{N(CH2PPh2)3-ÿ3 P}] (7). This compound was
at room H NMR (C6D6, 400 MHz, 353 K): ÿ 2.10 temperature over 5 days. (s,
1 previously reported.48 It should be noted that the complex slowly reacts with
(m, 25H, Ph), 7.35ÿ7.49 (m, 6H, CH2 tmm), 3.92 (s, 6H, NCH2P), 6.75ÿ7.09
CDCl3 at room temperature. Crystals suitable for X-ray diffraction analysis were
5H, Ph). 31P{1 H} NMR (C6D6, 162 MHz, 353 K): ÿ 19.1 (s). HRMS (ES): m/z
grown from a concentrated toluene solution left to stand at room temperature
calcd for C43H43NP3 102Ru ([M + H]+ ) 768.1652; found 768.1723. Anal. Calcd
overnight.
for C43H42NP3Ru (found): C, 67.35 (67.28); H, 5.52 (5.48); N, 1.83 (1.79).
[Ru(CO)3{N(CH2PCyp2)3-ÿ2 P}] (8). To a solution of 2 (386 mg, 0.685
mmol) in toluene (15 mL) was added [Ru3(CO)12] (146 mg, 0.228 mmol), and
the solution was stirred under reflux for 18 h, initially turning very dark before
[Ru(tmm){N(CH2PCyp2)3-ÿ3 P}] (4). To a solution of 2 (89.2 mg, 0.158
becoming lighter red. Removal of the solvent in vacuo and treatment of the
mmol) in toluene (5 mL) was added [Ru(COD)(methylallyl)2] (50.4 mg, 0.158
resulting residue with methanol
mmol), and the solution was stirred under reflux for 16 h. Cooling the solution
(10 mL) caused precipitation of an orange powder, which was isolated, washed
to room temperature overnight resulted in the formation of orange crystals that
with methanol (2 × 3 mL), and dried in vacuo. Dissolving the solid in
were isolated via filtration, washed with methanol (3 × 2 mL), and dried in vacuo
dichloromethane (5 mL) and layering this solution with methanol (15 mL) and
(22.3 mg, 0.0310 mmol, 20%).
1 allowing it to stand at room temperature overnight afforded bright orange
H NMR (CDCl3, 400 MHz): ÿ 1.23 (s, 6H, CH2 tmm),
crystals suitable for X-ray diffraction experiments (241 mg, 0.322 mmol, 47%).
1.31ÿ1.67 (m, 36H, CH2 Cyp), 1.80ÿ1.90 (m, 12H, CH2 Cyp), 2.04ÿ2.13 (m, 1
H NMR (C6D6, 400 MHz):
6H, CHCyp), 3.28 (s, 6H, NCH2P). 13C{1 H} NMR (CDCl3, 101 MHz): ÿ
ÿ 1.32ÿ1.92 (m, 50H, CHCyp and CH2 Cyp), 2.02ÿ2.14 (m, 4H, CHCyp), 2.45
25.7ÿ26.0 (m, CH2 Cyp), 29.6 (s, CH2 Cyp), 31.0 (s, CH2 Cyp), 35.6ÿ36.1 (m,
(s, 2H, NCH2P), 2.66 (s, 4H, NCH2P). 13C NMR (C6D6, 101 MHz): ÿ 26.3 (m,
CH2 tmm), 46.6ÿ46.7 (m, CHCyp), 51.2ÿ 51.6 (m, NCH2P), 102.8 (s, Ctmm).
CH2 Cyp), 26.6 (t, JCP = 4.6 Hz, CH2 Cyp), 26.7 (d, JCP = 6.5 Hz, CH2 Cyp),
31P{1 H} NMR (CDCl3, 162 MHz): ÿ 14.2 (s). HRMS (ES): m/z calcd for
29.4 (br s, CH2 Cyp), 30.7 (t, JCP = 13.2 Hz, CH2 Cyp), 35.7 (d, JCP = 12.2
C37H67NP3 102Ru ([M + H]+ ) 720.3530, found 720.3569. Anal. Calcd for 1
Hz, CHCyp-bound phosphorus), 40.7 JCP = 12.0 Hz, CHCyp-unbound
C37H66NP3Ru (found): C, 61.81 (61.76); H, 9.25 (9.30); N, 1.95 (1.89). 1 1
= 7.6phosphorus),
Hz, NCH2P-bound),
58.2 (dt, 215
(t, JCP
(t, JCP
= 17.0
= 8.7
Hz,Hz,
JCPCO).
= 9.7
31PHz,
NMR
JCP(C6D6, 162
3 1
MHz): ÿ ÿ19.9
JCP = 8.7(s,Hz,
1P,NCH2P-unbound),
unbound P), 29.0 65.2 (q,PÿRu). FT-IR (ÿ/ cmÿ13): carbonyl
(s, 2P,
[Ru(H)2(PPh3){N(CH2PPh2)3-ÿ3 P}] (5). To a solution of 1 (219 mg, 0.358 2
stretches 1867, 1902, 1978. HRMS (ES): m/z found 795.3019 (100%), 754.2841
mmol) in toluene (10 mL) was added [RuH2(PPh3)4] (412 mg, 0.358 mmol),
( 60%). Anal. Calcd for C36H60NP3O3 (found): C, 57.74 (57.81); H, 8.08 (7.98);
the Schlenk flask was wrapped in silver foil, and the solution was stirred at room
N, 1.87 (1.95).
temperature for 1 h, before the temperature was raised to 50 °C and stirred for
a further 11 h. The solvent was removed in vacuo and the yellow residue
extracted with diethyl ether (3 × 5 mL). Concentrating the ether solution and
[Ru(CO)2(OTf){N(CH2PPh2)3-ÿ3 P}](OTf) (9). To a solution of 7 (124 mg,
allowing it to stand at room temperature overnight gave yellow crystals suitable
0.162 mmol) in CH2Cl2 (5 mL) was added AgOTf (83.2 mg, 0.324 mmol),
for X-ray diffraction analysis (189 mg, 0.193 mmol, 54%).
1H resulting in instantaneous precipitation of Ag(s). The resulting suspension was
stirred for 1 h at room temperature. A pale yellow solution was filtered from the
NMR (C6D6, 400 MHz): ÿ ÿ7.73 (m, 2H, RuÿH), 3.93ÿ4.10 (m, 6H, NCH2P),
suspension via cannula, layered with diethyl ether (5 mL), and cooled to ÿ20 °C
6.65ÿ7.97 (m, 45H, Ph). 13C{1 H} NMR (C6D6, 101 MHz): ÿ 52.8 (m, NCH2P),
59.1 (m, NCH2P), 127.2ÿ128.0 (m, CHPh), 128.3 (d, JCP = 6.6 Hz, CHPh), overnight. A yellow microcrystalline powder was isolated, washed with diethyl
ether (3 × 3 mL), and dried in vacuo overnight (110 mg, 0.103 mmol, 64%).
132.2 (d, JCP = 10.7 Hz, CHPh), 133.1 (t, JCP = 5.6 Hz, CHPh), 133.9 (t, JCP 1H
= 7.1 Hz, CHPh), 134.5 (d, JCP = 11.2 Hz, CHPh), 142.0 (t , JCP = 15.7 Hz,
NMR (CD2Cl2, 400 MHz): ÿ 4.57 (s, 2H, NCH2P), 4.84 (app q, 4H, JHP = 11.6
CPh), 143.2 (d, JCP = 38.8 Hz, CPh), 144.6 (d, JCP = 34.4 Hz, CPh). 31P{1 H}
Hz, NCH2P), 7.04ÿ7.73 (m, 30H, Ph). 13C{1 H} NMR (CD2Cl2, 101 MHz): ÿ
NMR (C6D6, 162 MHz): ÿ 8.6 (dt, JPP = 1 3
2 2 2 49.7 (td, JCP = 5.7 Hz, NCH2Pcis), 53.6 (dt,
JCPJCP
= 12.3
= 5.2Hz,
Hz, NCH2Ptrans), 119.1
JPP = 25.9 Hz, 2P, Pcis), 27.3 (dt, JPPh3 = 210.8 Hz,
JCP = 17.4 Hz, (qd, JCP1JCF
= 2.38
= 319.3
Hz, bound3
Hz, CF3), 121.5 (q, JCF = 319.2 Hz,
2 2
27.8 Hz, 1P, Ptrans), 57.8 (dt, JPPh3P = 210.0 Hz, JPPh3P = 25.3 Hz, 1P, unbound
1
CPh),
CF3),
130.4
129.5
( t, (t,
JCP 4
JCP= 5.1
= 5.1
Hz,Hz,
CPh),
CPh),
131.9
129.9
(m,(d,CPh),
JCP 132.3
= 10.9(d,
1
Hz,JCP = 9.5
PPh3). FT-IR (ÿ/cmÿ1 ): hydride stretches 1915, 1882. HRMS (ES): m/z calcd Hz, CPh), 132.4 (s), 132.8 (d, JCP = 2.5 Hz, CPh), 133.2 (d, JCP = 4.5 Hz,
for C57H52NP4 102Ru ([M ÿ H]+ ) 976.2094, found 976.2083. CPh), 189.6 (m, CO). 31P{1 H} NMR (CD2Cl2, 162 MHz): ÿ ÿ23.9 (d, 2P, JPP
Anal. Calcd for C57H53NP4Ru (found): C, 70.07 (69.92); H, 5.47 (5.40); N, 1.43 = 19.5 Hz Ptrans). 19F{1 H} NMR (CD2Cl2, 376 MHz): ÿ ÿ78.5 (br s, 3F,
(1.47). unbound CF3), ÿ76.8 (s, 3F, bound CF3). FT-IR (ÿ/cmÿ1 ): carbonyl stretches
[Ru(H)2(PPh3){N(CH2PCyp2)3-ÿ3 P}] (6). To a solution of 2 (108 mg, 0.192 2055, 2095; trifluoromethyl 2CÿFJPP stretches
= 19.5 Hz,1158
Pcis),
(br),
19.6
1203(t, 1P, 2
(br), 1228 (br), 1279
mmol) in toluene (10 mL) was added [RuH2(PPh3)4] (221 mg, 0.192 mmol), (br); others 998, 1028, 1436. HRMS (ES): m/z calcd for C42H36NP3O5SF3
and the solution was stirred at room temperature for 2 h before being heated to 102Ru ([M ÿ OTf]+ ) 918.0523, found 918.0541. Anal. Calcd for
50 °C for 14 hours. The solvent was removed in vacuo, and the black-brown C43H36NP3O8S2F6Ru (found): C, 48.41 (48.54); H, 3.40 (3.35); N, 1.31 (1.29).
residue was washed with acetone (4 × 5 mL), forming an off-white/yellow
powder that was dried in vacuo (61.5 mg, 66.2 ÿmol, 35%).
1
H NMR (C6D6, 500
MHz): ÿ ÿ9.72 (m, 2H, RuÿH), 0.96ÿ2.66 (m, 54H, Cyp), 3.24 (m, 4H, NCH2P),
3
3.32 (br s, 2H, NCH2P ), 7.00 (dt, JHP = 1.2 Hz, 3H, CHparaÿPh), Hz, 5
JHH = 7.47.10ÿ7.13 [RuH(CO)2{N(CH2PPh2)3-ÿ3 P}](OTf) (10). A solution of 9 (65.0 mg, 60.9
3 3
(dt, JHH = 7.9 Hz, JPH = 1.5 Hz, 6H, CHorthoÿPh), 8.25ÿ8.29 (m, 6H, CHmeta ÿmol) in THF (5 mL) was placed under 3 bar of H2 in a sealed ampule, heated
-Ph). 13C{1 H} NMR (C6D6, 126 MHz): ÿ 25.0 (s, CH2 Cyp), 26.1 (t, JCP = 5.0 to 70 °C, and stirred vigorously for 17 h, resulting in a color change from yellow
Hz, CH2 Cyp), 26.2 (d, JCP = 9.1 Hz, CH2 Cyp), 26.8 ( s, CH2 Cyp), 26.9 (t, to colorless. The solvent was removed in vacuo, and the resulting residue was
JCP = 3.1 Hz, CH2 Cyp), 27.5 (d, JCP = 6.4 Hz, CH2 Cyp), 28.7 (s, CH2 Cyp), washed with diethyl ether (4 × 5 mL), forming an off-white powder that was dried
29.4 (s, CH2 Cyp), 29.6 ( s, CH2 Cyp), 29.9 (s, CH2 Cyp), 30.7 (s, CH2 Cyp), in vacuo overnight (39.8 mg, 0.0433 mmol, 71%).
1
31.0 (s, CH2 Cyp), 51.0ÿ51.1 (m, NCH2P), 45.9 (d, JCP = 21.7 Hz, CHCyp) , H NMR (THF-d8, 500 MHz):
2
1
47.3 (t, JCP = 8.7 Hz, CHCyp), 127.0 (d, JCP = 8.1 Hz, CHmetaÿPh), 127.51(s, ÿ ÿ6.75 (dt, 1H, 4.45 (dd, JHPcis = 14.5 Hz, 2JHPtrans = 60.6 Hz, RuÿH),
3 2
CHparaÿPh), 134.7 (d, JCP = 11.4 Hz, CHorthoÿPh) 147.1 (d, JCP = 29.6 Hz 4H, NCH2P), JHP = 15.4 Hz, J = 71.6 Hz, NCH2P), 4.89 (s, 2H,
2
CPh). 31P{1 H} NMR (C6D6, 202 MHz): ÿ ÿ5.3 (dt, JPP = 25.3 Hz, 1 6.92ÿ7.66 (m, 30H, Ph). 13C{1 H} NMR (THF-d8, 101 MHz): ÿ 51.2ÿ51.6 (m,
2
NCH2P), 122.2 (q, JCF = 320.4 Hz, CF3),

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Inorganic Chemistry Article

129.6 (t, JCP = 4.8 Hz, CHPh), 130.2 (d, JCP = 10.1 Hz, CHPh), 131.1 (d, was washed through with additional acetonitrile (2 × 2 mL). The solution was
JCP = 12.7 Hz, CHPh), 132.5 (t, JCP = 5.0 Hz, CHPh), 132.8 ( d, JCP = 11.3 stirred at room temperature for 2 h, before the solvent was removed in vacuo,
Hz, CHPh), 133.9 (t, JCP = 5.0 Hz, CHPh), 134.8 (d, JCP = 21.7 Hz, CPh), affording the intermediate [RuH(CO)- (MeCN)N(CH2PPh2)3-ÿ3 P}] (13) as a
136.8 (d, JCP = 36.6 Hz, CPh), 197.3ÿ198.3 ( m, CO). 31P{1H } brown powder that was washed with hexane (3 × 3 mL) and dried in vacuo
2
NMR (THF-d8, 162 MHz): ÿ ÿ16.8 (t, 1P, JPP = 25.5 Hz, Ptrans), JPP = 25.5 for 30 min.
2
ÿ79.2 (s). FT- Hz, Pcis). 19F NMR (THF-d8, 470 MHz): ÿ ÿ2.01 (d, 2P, Intermediate 13 was dissolved in degassed acetone-d6 (0.5 mL), and H NMR
1 1
IR (ÿ/cmÿ1 ) : carbonyl stretches 2004, 2051; trifluoromethyl CÿF stretches H and 31P{1 H} NMR spectra were recorded. (400 initial
2 2
1025 (br ) . _ _ .Anal. MHz, acetone-d6): ÿ ÿ6.30 (ddd, 1H, JHP =JHP 16.4=Hz,
77.5Hz,
RuÿH). 31P{1 H} NMR
(162 MHz, acetone-d6): ÿ ÿ144.2 (septet, 1P, JPP = 31.6 Hz,
1 2 2
JPF = 708.4 Hz, PF6 ÿ), ÿ12.4 (m), 3.9 (dd, 1P, JPP = 27.5 Hz), 26.5 (dd,
2 2
Calcd for C43H36NP3O8S2F6Ru (found): C, 54.90 (54.81); H, 4.06 (4.12); 1P, JPP = 22.3 Hz). In the NMRJPP =tube
32.4was
Hz,placed a solution of levulinic acid
N, 1.52 (1.62). (10.8 mg, 93.0 ÿmol, 1.43 equiv) in degassed acetone-d6 (0.5 mL), and the
[Ru(CO3)(CO){N(CH2PPh2)3-ÿ3 P}] (11). Method A. A partially dissolved solution was stirred H and 31P{1 H} NMR spectra were for 2 min using to
1
suspension of 7 (280 mg, 0.364 mmol) in toluene (5 mL) was bubbled with h, with the first being taken vortex stirrer. recorded every 1 h for 16
O2 for 10ÿ15 min. The orange precipitate that formed was collected by approximately 10 min after stirring. The reaction was complete within 21 h.
1H NMR
filtration, washed with toluene (2 × 3 mL) and diethyl ether (2 × 3 mL), and
3
dried in vacuo (204 mg, 0.255 mmol, 70%). Crystals suitable for _ 6.92ÿ7.72 (400 MHz, acetone-d6): ÿ 2.23 (s, 3H, CH3 LA), 2.67 (t, 2H, Hz, JHH = 5.8
3
(m, 30H, Ph). 13C{1 H} NMR (CDCl3, 101 MHz): ÿ 50.1 (dt, JCP = 6.2 Hz, CH2 LA), 2.84 (t, 2H, JHH = 5.9 Hz, CH2 LA), 4.55ÿ4.68 (m, 6H, NCH2P),
NCH2Ptrans), 51.1 (td, JCP = 12.5 JCP = 3.2 Hz, NCH2Pcis), 128.2 (d, JCP 6.95ÿ7.68 (m, 30H, Ph). 13C{1 H} NMR (101 MHz, acetone-d6): ÿ 28.1 (s,
1
129.8 = 6.8 Hz, CHPh), 128.5ÿ Hz, 128.7 (m, CHPh), 129.4 (br s, CHPh), CH3 LA), 37.5 (CH2 LA), 38.2 (s, CH2 LA), 50.7 (td,
1 3 1
(s, CHPh), 130.1 (s, CHPh), 130.9 (t, JCP = 5.0 Hz, CHPh), 132.5 ( d, JCP JCP = 13.2 Hz, JCP = 5.4 Hz, NCH2P), 51.7 (dt, JCP = 19.1 Hz,
1 3 1 3
= 9.3 JCPHz, CHPh),
= 18.5Hz,
132.8 (t, JCP = 4.9 Hz, CHPh), 133.3ÿ134.0 (m, CPh), JCP = 5.4 Hz, NCH2P), 129.1 (d, JCP = 9.6 Hz, CHPh), 131.0 (d, JCP =
3
Hz, 136.2ÿ136.9 (m, CPh), 167.8 (s, CO3), 194.0 (dt , JCPtrans = 106.4 2.6, CHPh), 131.6 (s, CHPh), 131.9 (s, CHPh), 132.0 (t, JCP = 5.1 Hz,
2JCPcis = 11.0 Hz, CO). 31P{1 H} NMR (CDCl3, 162 MHz): ÿ ÿ23.5 (t, Pcis), CHPh), 133.2 (t, JCP = 4.6 Hz, CHPh), 133.7 (d, JCP = 9.5 Hz, CHPh),
15.9 (d, 174.0 (s, TAIL), 192.0 (s, TAIL), 206.7 (d, JCP = 3.0 Hz, CO).
2
31P{1 H} NMR (162 MHz, acetone-d6): ÿ ÿ16.2 (dd, JPP = 26.4 Hz, Ptrans),
2 2
19.8 (dd, JPP = 26.4 Hz, Pcis). MS (ES): m/z calcd for C45H43NP3O4
2
JPP = 33.8 Hz, 102Ru ([M ÿ PF6] + ) 856.1, found 856.4.
2
JPP = 33.3 Hz, Ptrans). FT-IR (ÿ/cmÿ1 ): carbonyl stretch
1994; ÿ2 -carbonate stretches 1565, 1434; ÿ2 -carbonate bends 1272, 1092; ÿ ASSOCIATED CONTENT
others 1485. HRMS (ES): m/z calcd for C41H37NP3O4 102Ru ([M + H]+)
802.0979, found 802.1005. Anal. Calcd for C41H36NP3O4Ru (found): C,
*S Supporting Information
61.50 (61.27); H, 4.53 (4.34); N, 1.75 (1.84). Figures, tables, and CIF files giving 31P{1 H} NMR spectra of
ligand 2, complexes 3ÿ12, and intermediate 13, a comparison
Method B. A sample of 7 (63.4 mg, 0.0825 mmol) was deliberately and of the hydride region1 of H 1 H{31P} NMR spectra of 5
exposed to air for 5 weeks. Washing with wet toluene (5 × 1 mL) and wet and 6, and additional crystallographic data, including 50%
diethyl ether (5 × 1 mL) and drying in air afforded a yellow-brown powder probability ellipsoid ORTEP diagrams of all independent crystal
with characterization data identical with those produced via method A (48.0 structures. This material is available free of charge via the
mg, 59.9 ÿmol, 73%) .
Internet at http://pubs.acs.org.
[Ru(H)2(CO){N(CH2PPh2)3-ÿ3 P}] (12). A solution of 11 (763 mg, 0.953
mmol) in THF (25 mL) was injected into a high-pressure reactor under a flow
ÿ AUTHOR INFORMATION
of nitrogen. The atmosphere was changed to hydrogen and pressurized to
15 bar at room temperature before the mixture was heated to 100 °C Corresponding Authors
(increasing the internal pressure to ca. 20 bar) and stirred for 2 h. After the *E-mail for NJL: [email protected].
mixture was cooled to room temperature, the gas was carefully vented and *E-mail for PWM: [email protected].
the atmosphere changed to nitrogen. The solution was transferred from the Author Contributions
reactor to a Schlenk flask, filtered, and diluted with methanol (20 mL), and
the solvent was removed in vacuo, giving an orange powder that was washed The manuscript was written through contributions of all authors.
with methanol (3 × 5 mL) and diethyl ether ( 3 × 5 mL) and dried in vacuo All authors have given approval to the final version of the
(365 mg, 0.492 mmol, 52%). Crystals suitable for X-ray diffraction analysis manuscript. NJB assisted in setting up the high-pressure
were grown from a concentrated toluene solution layered with H NMR (C6D6, reactor and initial hydrogenation reactions. AJPW was primarily
400 MHz): ÿ ÿ6.50 (dd, 2H, methanol. responsible for the X-ray crystallographic analysis.
1 2
JHPtrans Notes
2
49.3 Hz, = JHPcis = 18.8 Hz, RuÿH), 3.66 (s, 2H, NCH2P), 3.82 (m, 4H,
NCH2P), three multiplets 6.69ÿ6.87, 7.27ÿ7.34 and 7.51ÿ7.61 (m, 30H , Ph).
The authors declare no competing financial interest.
13C{1 H} NMR (C6D6, 101 MHz): ÿ 51.8 (m, NCH2P), 53.5 (m, NCH2P),
ÿ ACKNOWLEDGMENTS
127.7ÿ128.3 (m, CHPh), 128.5 (d, JCP = 11.2 Hz, CHPh), 131.8 (t, JCP =
6.2 Hz, CHPh), 132.5 (d, JCP = 12.0 Hz, CHPh), 132.9 (t, JCP = 6.9 Hz, We thank Imperial College London for funding, via the
CHPh), 138.6 (dt, JCP = 38.8 Hz, JCP = 3.5 Hz, CPh ), 139.6 (m, CPh) Frankland Chair endowment. Johnson Matthey plc are also
2
141.0 (m, CPh), 209.2 (dt, JCPtrans = 73.7 Hz,
2 2
thanked for the loan of the precious-metal salts used in this
JCPcis = 8.3, CO). 31P{1 H} NMR (C6D6, 162 MHz): ÿ 8.5 (d, JPP = 35.7 work.
2
Hz, 2P), 18.8 (t, JPP = 34.8 Hz, 1P). FT-IR (ÿ/cmÿ1 ): RuÿCO and RuÿH
stretches 1858, 1926, 2190. MS (ES) m/z calcd for C40H38NP3O102RuK
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