Nitrous oxide mediated synthesis of monomeric hydroxoruthenium complexes. Reactivity of (DMPE)2Ru(H)(OH) and the synthesis of a silica-bound ruthenium complex

Article abstract of DOI:10.1021/om980295d

Treatment of (DMPE)₂Ru(H)₂ with 1 equiv of N₂O affords the hydroxoruthenium complex (DMPE)₂Ru(H)(OH) (1) in 41% yield. Further treatment with an excess of N₂O affords the dihydroxo complex (DMPE)₂Ru(OH)₂ (5) in 30% yield. Addition of phenols, thiols, and silanols to 1 yields the corresponding aryloxo-, thiolato-, and siloxoruthenium complexes 6-10 in 25-75% yield. The hydroxo ligand of 1 may also be exchanged with the surface silanols of silica to form the silica-bound complex (DMPE)₂Ru(H)(OSilica) (14). Subsequent treatment of 14 with thiocresol removes the ruthenium complex as (DMPE)₂Ru(H)(SC₆H₄Me) (10). The treatment of 1 with acetone affords the C-bound enolate complex (DMPE)₂Ru(H)(CH₂C(O)CH₃) (15) in 34% yield. Terminal alkynes react with 1 to give the ruthenium acetylide complexes trans-(DMPE)₂Ru(H)(CCPh) 16 (74% yield) and trans-(DMPE)₂Ru(H)(CCH) 17 (32% yield). Reactivity may also be affected at both ends of 1,7-octadiyne to give the bimetallic complex (DMPE)₂RuC≡C(CH₂)₄C≡CRu(DMPE) ₂ (19, 33% yield). The addition of Ph₃SnH, which does not contain an acidic hydrogen, to 1 affords (DMPE)₂Ru(H)(SnPh₃) (20) in 32% yield. When 1 is treated with 1 equiv of p-tolualdehyde, the hydroxo oxygen is retained, the aldehydic C-H bond is broken, and the ruthenium carboxylate complex (DMPE)₂Ru(H)(OC(O)C₆H₄CH₃) (21) is obtained in 28% yield. The structural assignment of 21 was confirmed by X-ray crystallography. Similar reactivity is observed when 1 is treated with hexafluoroacetone, in which case the C-C bond is cleaved to produce (DMPE)₂Ru(H)(OC(O)CF₃) (22, 55% yield). Much of the observed reactivity of 1 is rationalized using the assumption that the first step involves reversible formation of a metal cation/OH_- ion pair (23). Attempts to trap the cation with ethylene resulted in formation of the ruthenium ethylene complex (DMPE)₂Ru(C₂H₄) (2); there is strong evidence that 2 forms via a cationic hydridoruthenium ethylene complex. Treatment of 1 with CO forms the cationic hydrido carbonyl complex [(DMPE)₂Ru(H)(CO)][OH] (25).

Full text of DOI:10.1021/om980295d

5072
Organometallics 1998, 17, 5072-5085
Nitr ou s Oxid e Med ia ted Syn th esis of Mon om er ic
Hyd r oxor u th en iu m Com p lexes. Rea ctivity of
(DMP E)2Ru (H)(OH) a n d th e Syn th esis of a Silica -Bou n d
Ru th en iu m Com p lex
Anne W. Kaplan and Robert G. Bergman*
Department of Chemistry, University of California, Berkeley, California 94720
Received April 17, 1998
Treatment of (DMPE)2Ru(H)2 with 1 equiv of N2O affords the hydroxoruthenium complex
(DMPE)2Ru(H)(OH) (1) in 41% yield. Further treatment with an excess of N2O affords the
dihydroxo complex (DMPE)2Ru(OH)2 (5) in 30% yield. Addition of phenols, thiols, and silanols
to 1 yields the corresponding aryloxo-, thiolato-, and siloxoruthenium complexes 6-10 in
25-75% yield. The hydroxo ligand of 1 may also be exchanged with the surface silanols of
silica to form the silica-bound complex (DMPE)2Ru(H)(OSilica) (14). Subsequent treatment
of 14 with thiocresol removes the ruthenium complex as (DMPE)2Ru(H)(SC6H4Me) (10). The
treatment of 1 with acetone affords the C-bound enolate complex (DMPE)2Ru(H)(CH2C(O)-
CH3) (15) in 34% yield. Terminal alkynes react with 1 to give the ruthenium acetylide
complexes trans-(DMPE)2Ru(H)(CCPh) 16 (74% yield) and trans-(DMPE)2Ru(H)(CCH) 17
(32% yield). Reactivity may also be affected at both ends of 1,7-octadiyne to give the
bimetallic complex (DMPE)2RuCtC(CH2)4CtCRu(DMPE)2 (19, 33% yield). The addition
of Ph3SnH, which does not contain an acidic hydrogen, to 1 affords (DMPE)2Ru(H)(SnPh3)
(20) in 32% yield. When 1 is treated with 1 equiv of p-tolualdehyde, the hydroxo oxygen is
retained, the aldehydic C-H bond is broken, and the ruthenium carboxylate complex
(DMPE)2Ru(H)(OC(O)C6H4CH3) (21) is obtained in 28% yield. The structural assignment
of 21 was confirmed by X-ray crystallography. Similar reactivity is observed when 1 is
treated with hexafluoroacetone, in which case the C-C bond is cleaved to produce
(DMPE)2Ru(H)(OC(O)CF3) (22, 55% yield). Much of the observed reactivity of 1 is
rationalized using the assumption that the first step involves reversible formation of a metal
cation/OH- ion pair (23). Attempts to trap the cation with ethylene resulted in formation
of the ruthenium ethylene complex (DMPE)2Ru(C2H4) (2); there is strong evidence that 2
forms via a cationic hydridoruthenium ethylene complex. Treatment of 1 with CO forms
the cationic hydrido carbonyl complex [(DMPE)2Ru(H)(CO)][OH] (25).
In tr od u ction
to be important in the hydration of olefins to alcohols,
the hydration of nitriles to carboxamides, and the
Wacker process.3,24-27
The preparation and characterization of the mono-
meric hydroxoruthenium complex (DMPE)2Ru(H)(OH)
(1) via the oxidative addition of water to the Ru(0)
Many catalytic processes involve intermediates that
are proposed to contain late-transition-metal-heteroa-
tom (N, O, S) bonds.1-3 Recent work has been directed
toward the synthesis of these potentially reactive spe-
cies, but there remain few examples of monomeric late-
metal hydroxo complexes,3-23 species which are thought
(12) Mehrotra, R. C.; Agarwal, S. K.; Singh, Y. P. Coord. Chem. Rev.
1985, 68, 101.
(1) Masters, C. Homogeneous Transition-Metal Catalysis; Chapman
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1997, 16, 5342.
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229.
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Chem. 1978, 161, 75-90.
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7888.
(19) Edwards, A. J .; Elipe, S.; Esteruelas, M. A.; Lahoz, F. J .; Oro,
L. A.; Valero, C. Organometallics 1997, 16, 3828.
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Dalton Trans. 1976, 1995.
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3941.
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Soc. 1989, 111, 2717.
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1986, 108, 6387.
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tallics 1997, 16, 5601.
(23) Bryndza, H. E.; Fong, K. L.; Paciello, R. A.; Tam, W.; Bercaw,
J . E. J . Am. Chem. Soc. 1987, 109, 1444.
10.1021/om980295d CCC: $15.00 © 1998 American Chemical Society
Publication on Web 10/16/1998

Monomeric Hydroxoruthenium Complexes
Organometallics, Vol. 17, No. 23, 1998 5073
Sch em e 1
complex (DMPE)2Ru(C2H4) (2) to form [(DMPE)2Ru(H)-
(OH)]2‚2H2O (3) and subsequent removal of the hydrogen-
bound H2O with 4 Å molecular sieves has been reported.
Elevated temperatures and extended reaction times are
necessary to effect this reaction.28 More recently we
have shown that 1 may be prepared under milder
conditions from (DMPE)2Ru(H)2 (4) and N2O.29 This
transformation represents the first example of oxygen
atom transfer from N2O into a late-transition-metal-
hydrogen bond. We now report the full details of the
synthesis of 1, outline its reactivity patterns, and
describe the synthesis and chemistry of a silica-bound
ruthenium complex.
Resu lts
Syn t h esis of Mon om er ic H yd r oxor u t h en iu m
Com p lexes. Hillhouse and co-workers have found that
N2O can be used to insert oxygen atoms into nickel-
carbon and the relatively oxophilic (group 4) early-
metal-hydrogen bonds.30-34 We have found that N2O
can be used to mediate oxygen atom insertion into the
Ru-H bond of (DMPE)2Ru(H)2 (4) (eq 1). Treatment
tan to light brown. Decomposition to multiple products
is observed upon warming to 75 °C.
Rea ctivity of Mon om er ic Hyd r oxor u th en iu m
Com p lexes tow a r d P r otic Rea gen ts. We have stud-
ied the exchange chemistry of 1 and have demonstrated
that a number of complexes containing ruthenium-
heteroatom bonds are accessible by treatment with
protic reagents at room temperature. Addition of phe-
nols, thiols, and silanols to 1 yield the corresponding
aryloxo-, thiolato-,35 and siloxoruthenium complexes
6-10 in 25-75% yield (Scheme 1).36 These reactions
all occur at room temperature in benzene, and the
products exhibit many diagnostic spectroscopic features.
The 1H NMR spectrum of the phenoxide 6 shows a
hydride resonance at δ -23.3 ppm as a quintet (J HP
)
21.8 Hz). A trans geometry is indicated by 31P{1H}
NMR spectroscopy, which shows a single resonance at
δ 45.4 ppm for the equivalent phosphine groups. The
M-H stretch is observed at 1928 cm-1 in the IR
spectrum. Similar characteristics are observed for
complexes 7-10. Hydrido aryloxide and thiolate com-
plexes are also accessible by treating (DMPE)2Ru(C2H4)
with aryl alcohols and thiols (Scheme 1); however,
elevated temperatures and longer reaction times are
necessary (see Discussion).
of the dihydride with 1 equiv of N2O affords the
hydroxoruthenium complex 1 in 41% yield after crystal-
lization. Treatment of either dihydride 4 or the isolated
monoinsertion product 1 with 1 atm of N2O affords the
dihydroxo complex (DMPE)2Ru(OH)2 (5), which can be
obtained 95% pure in 30% yield (eq 1). Other oxygen
atom transfer agents such as pyridine N-oxide, Me3NO,
and ethylene oxide do not react with 4 in benzene up to
135 °C, at which point decomposition is observed.
In the reaction of 1 with thiocresol, excess thiol reacts
with the hydrido thiolate product 10 to form a 3:1
mixture of cis and trans bis(thiolate) complexes with the
loss of H2 (Scheme 2). Complex 11 can also be obtained
by treating (DMPE)2Ru(Et)(SC6H4Me) with 1 equiv of
HSC6H4Me; the ratios of cis to trans isomers obtained
is again 3:1. Pure trans-(DMPE)2Ru(SC6H4Me)2 can be
crystallized selectively as red, air-stable blocky crystals
by diffusion of pentane into a toluene solution of the
two isomers at room temperature. Isolation of trans-
11 by crystallization made it possible to assign proton
The hydroxo complexes 1 and 5 are sensitive to air.
Both are stable to a few equivalents of water but
decompose to multiple products upon dissolution in neat
water. No observable decomposition is detected spec-
troscopically when 1 and 5 are treated with 1 equiv of
oxygen in benzene, although the solutions darken from
(24) J ensen, C. M.; Trogler, W. C. J . Am. Chem. Soc. 1986, 108, 723.
(25) Bennett, M. A.; Yoshida, T. J . Am. Chem. Soc. 1973, 95, 3030.
(26) Bottomley, F.; Sutin, L. Adv. Organomet. Chem. 1988, 28, 339.
(27) Yoshida, T.; Matsuda, T.; Okano, T.; Otsuka, S. J . Am. Chem.
Soc. 1979, 101, 2027.
(28) Burn, M. J .; Fickes, M. G.; Hartwig, J . F.; Hollander, F. J .;
Bergman, R. G. J . Am. Chem. Soc. 1993, 115, 5875.
(29) Kaplan, A. W.; Bergman, R. G. Organometallics 1997, 16, 1106.
(30) Koo, K.; Hillhouse, G. L.; Rheingold, A. L. Organometallics
1995, 14, 456.
(31) Matsunaga, P. T.; Hillhouse, G. L. J . Am. Chem. Soc. 1993,
115, 2075.
(32) Matsunaga, P. T.; Mavropoulos, J . C.; Hillhouse, G. L. Polyhe-
dron 1995, 14, 175.
1
resonances in the H NMR spectrum for both isomers.
In the case of trans-11, the equivalent phosphine methyl
protons appear at δ 1.35 ppm. The 31P{1H} NMR
spectrum of trans-11 shows a singlet for the equivalent
phosphines at δ 36.4 ppm. The cis isomer of 11 shows
a
1H NMR spectrum similar to that of trans-11; 31P-
(33) Vaughan, G. A.; Rupert, P. B.; Hillhouse, G. L. J . Am. Chem.
Soc. 1987, 109, 5538.
(34) Vaughan, G. A.; Sofield, C. D.; Hillhouse, G. L. J . Am. Chem.
Soc. 1989, 111, 5491.
(35) Burn, M. J .; Fickes, M. G.; Hollander, F. J .; Bergman, R. G.
Organometallics 1995, 14, 137.
(36) Yields refer to recrystallized material and do not reflect percent
conversions to spectroscopically pure material, which are >90%.

5074 Organometallics, Vol. 17, No. 23, 1998
Kaplan and Bergman
Sch em e 2
Sch em e 3
{1H} NMR spectroscopy is more diagnostic. Two triplets
at δ 38.6 and 33.1 ppm (J PP ) 22.1 Hz) indicate a cis
orientation of the thiocresolate ligands. In an effort to
synthesize each isomer individually, cis- and trans-
(DMPE)2RuCl2 were each treated with an excess of
KSC6H4Me in toluene at 170 °C for 16 days. The rather
stringent conditions required for this metathesis also
effected the interconversion of cis and trans isomers,
giving the same 3:1 mixture (Scheme 2).
Sch em e 4
Because the reaction mixture was heterogeneous,
efforts were made to increase the solubility of the
potassium thiocresolate. THF was used as an alternate
solvent, but no reaction occurred at 105 °C, even in the
presence of 18-crown-6;37 therefore, this route was
abandoned. Lithium salts have been used to increase
the solubility of the anion in heterogeneous reaction
mixtures.38 The addition of lithium cresolate, however,
also had no effect on the reaction. Considering the
elevated temperatures at which the bis(thiolates) are
formed from the dichloride, the 3:1 cis-/trans-11 mixture
appeared to be the thermodynamic ratio. Thermolysis
of purified trans-11 in THF-d8 at 135 °C for 12 days
results in the same 3:1 ratio, which confirms this
conclusion. A similar ratio of bis(thiolate) complexes
was reported recently for the synthesis of (DMPE)2Ru-
(SPh)2 from (DMPE)2Ru(H)2.39
Silica a s a Liga n d . Metal oxide supported transi-
tion-metal complexes have drawn interest as hybrids
of heterogeneous and homogeneous catalysts.40-42 Mey-
er et al. previously reported that Cp*(PMe3)(Ph)Ir(OH)
(12) undergoes exchange with silica to form the sup-
ported complex Cp*(PMe3)(Ph)Ir[silica] (13, Scheme 3).43
More importantly, the iridium complex can be removed
from silica using phenols, forming the corresponding
phenoxide complexes. The reactivity of 1 toward protic
reagents suggested that a similar silica-bound ruthe-
nium complex may be accessible by treating 1 with
silica.
When silica is treated with hydroxoruthenium com-
plex 1 in THF, the new silica-bound complex 14 is
formed, the silica turns tan, and the supernatant
changes from tan to colorless (Scheme 4). Complex 14
is stable at room temperature. The 13C CPMAS NMR
spectrum of the supported complex 14 (see the Support-
ing Information) shows three resonances for the trans-
disposed DMPE ligands at δ 31, 21, and 14 ppm.
Interrupted decoupling experiments44 were employed to
identify the two upfield resonances as the CH3 carbons.
The 31P CPMAS NMR displays one singlet at δ 44.0 ppm
as expected, confirming the trans geometry and sup-
(37) Dall’Antonia, P.; Graziani, M.; Lenarda, M. J . Organomet.
Chem. 1980, 186, 131.
(38) Ito, Y.; Nakatsuka, M.; Kise, N.; Saegusa, T. Tetrahedron Lett.
1980, 21, 2873.
(39) Field, L. D.; Hambley, T. W.; Yau, B. C. K. Inorg. Chem. 1994,
33, 2009.
(40) Supported Metal Complexes; Hartley, F. R., Ed.; D. Reidel:
Boston, 1985.
(41) Yermakov, Y. I.; Kuznetsov, B. N.; Zakharov, V. A. Catalysis
by Supoprted Metal Complexes; Elsevier: New York, 1981.
(42) See, for example: (a) Dufour, P.; Scott, S. L.; Santini, C. C.;
Lefebvre, F.; Basset, J .-M. Inorg. Chem. 1994, 33, 2509. (b) Scott, S.
L.; Dufour, P.; Santini, C. C.; Basset, J .-M. Inorg. Chem. 1996, 35, 869.
(c) Scott, S. L.; Crippen, C.; Santini, C. C.; Basset, J .-M. J . Chem. Soc.,
Chem. Commun. 1995, 1875. (d) Scott, S. L.; Basset, J .-M.; Niccolai,
G. P.; Santini, C. C.; Candy, J .-P.; Lecuyer, C.; Quignard, F.; Choplin,
A. New J . Chem. 1994, 18, 115.
(43) Meyer, T. Y.; Woerpel, K. A.; Novak, B. M.; Bergman, R. G. J .
Am. Chem. Soc. 1994, 116, 10290.
(44) Opella, S. J .; Frey, M. H. J . Am. Chem. Soc. 1979, 101, 5854.

Monomeric Hydroxoruthenium Complexes
Organometallics, Vol. 17, No. 23, 1998 5075
Sch em e 5
porting the formation of one distinct silica-bound spe-
cies. For comparison, CPMAS spectra were also ob-
tained on a solid sample of 1 (see the Supporting
Information). The 13C CPMAS NMR spectrum of 1
contains resonances at δ 33, 24, and 14 ppm. The 31P
CPMAS NMR displays a singlet at δ 49 ppm. The IR
spectrum of 14 shows a weak M-H stretch at 1967
cm-1, which is close to that of 8 (1928 cm-1), whereas
the M-H stretch of 1 appears at 1836 cm-1. Interest-
ingly, it is also possible to obtain a conventional 31P-
{1H} spectrum of 14 as a “slurry”. When a 10 mm NMR
tube is loaded with a suspension of 14 in THF-d8, 31P-
{1H} analysis in 1000 scans shows a singlet at δ 47
ppm.45 The NMR resonances for 14 are only slightly
different from those of 1.
The solid-state characterization is consistent with the
proposed structure of 14. To obtain further evidence
for the structure of the supported complex, the reactivity
of 14 with thiocresol was exploited. The addition of
exactly 1 equiv of thiocresol to 14 produces hydrido
thiocresolate 10 in 95% yield (Scheme 4). Since these
exchange reactions presumably involve cleavage of only
the Ru-O bond, and hydroxidoruthenium complexes 1
and 10 are otherwise analogous, the structure of bound
ruthenium complex 14 may be inferred. Evidence that
the ruthenium complex is in fact chemisorbed by a
ruthenium-oxygen bond, and not simply hydrogen-
bonded to the silica surface, was obtained by monitoring
the reaction of (DMPE)2Ru(C2H4) (2) with silica (Scheme
4). The ruthenium-silica species formed from 2 and
silica exhibits the same solid-state spectroscopic data,
as well as reactivity toward thiocresol as the species
generated from 1 and silica. When this reaction is
followed by 1H NMR in THF-d8, 1 equiv of free ethylene
is observed.
Reactions that result in attachment and removal of
1 from the silica surface appear to leave the ruthenium
hydride linkage intact. When, however, an excess of
thiocresol is used in removing the ruthenium complex
from the surface, a mixture of bis(thiocresolates) cis- and
trans-11 is obtained, presumably by further reaction of
the initially formed cresolate hydride 10 with the excess
thiocresol (vide infra). Interestingly, 14 may be pre-
pared in benzene, but 14 is unreactive toward thiocresol
at room temperature in benzene, a trend also observed
in the reactions of iridium-silica complex 13 with
phenols. When the solvent is replaced with THF, 14
reacts with thiocresol as described above.
coupling of the carbon to the four equivalent phosphorus
atoms. In an O-bound structure, the CH2 would appear
as a singlet. Further, the 1H NMR shift of the CH2
group is at δ 1.57 ppm, which is not in the olefinic
region. Finally, the presence of a carbonyl is supported
by the downfield shift of δ 210.7 ppm in the 13C{1H}
NMR spectrum and an IR stretch at 1713 cm-1. It is
also interesting to note that the 1H chemical shift of the
hydride resonance reflects the trans influence of the
ligand located trans to it. For example, the chemical
shift of the hydride at δ -16.67 ppm is similar to that
observed for analogous bis-DMPE ruthenium alkoxides,
amides, and halides (δ -18 to -25 ppm) but is substan-
tially upfield from shifts observed when the H is trans
to a hydride, stannyl, or hydrocarbyl ligand (δ -9 to -13
ppm).
Terminal alkynes react with hydroxo hydride 1 to give
the ruthenium acetylide complexes 16 (74% yield) and
17 (32% yield) (Scheme 5).36 Complex 16 has been
generated independently from dihydride 4 and 1 equiv
of phenylacetylene. The H and alkynyl groups in
complexes 16 and 17 are also trans-disposed, as they
each contain a singlet in the 31P{1H} NMR spectrum at
δ 45.5 and 45.2 ppm, respectively. The hydrides appear
as quintets at δ -11.95 and -12.37 ppm in the 1H NMR
spectrum. The IR spectrum of 17 exhibits a CtC
stretch at 1905 cm-1
.
In the analogous doubly-13C-
labeled complex trans-(DMPE)2Ru(H)(13C13CH) (17-
13C2), the 13Ct13C stretch appeared at 1838 cm-1. The
monomeric nature of 17 is supported by EIMS and the
presence of a terminal C-H stretch at 3269 cm-1. The
13C{1H} NMR spectrum of 17-13C2 shows the terminal
acetylide carbon as a doublet at δ 91.2 ppm (J CC ) 110.6
Hz) and the ruthenium-bound acetylide carbon as a
doublet of quintets at δ 121.8 ppm (J CP ) 13.7 Hz). The
1H NMR spectrum of 17-13C2 shows the terminal acetyl-
ide proton as a doublet at δ 2.14 ppm (J HC ) 35.0 Hz).
Phenylacetylene also reacts with the dihydroxo complex
5 to give the bis(acetylide) complex 18. Bis(acetylide)
Tr ea tm en t of 1 w ith Ca r bon Acid s. Hydroxo
hydride 1 is also reactive toward molecules containing
acidic C-H bonds. For example, the treatment of 1 with
acetone affords the C-bound enolate complex 15 in 34%
yield (Scheme 5).36 The presence of a singlet in the 31P-
{1H} NMR spectrum at δ 43.0 ppm and two DMPE
1
methyl peaks in the H NMR spectrum at δ 1.38 and
1.14 ppm indicates a trans configuration. The hydride
appears as a quintet at δ -16.67 ppm, and the M-H
stretch in the IR is at 1928 cm-1. Confirmation that
the enolate is C-bound comes from the following data.
DEPT experiments confirm the presence of a CH2 group
which appears as a quintet (J CP ) 4.2 Hz), indicating
(45) A reviewer has suggested that the resonance may be due to a
solution species which has leached from the silica surface. This is
unlikely, since NMR analysis of the supernatant alone after taking a
spectrum of the suspension contains no detectable 31P resonances.
18 was recently reported by Field and co-workers to be

5076 Organometallics, Vol. 17, No. 23, 1998
Kaplan and Bergman
Ta ble 1. Cr ysta l Da ta for 21
the product of addition of phenyl acetylene to 4.46
Interestingly, reactivity can be effected at both ends of
1,7-octadiyne to give the bimetallic complex 19 in 33%
yield (Scheme 5). Complex 19 has been formulated as
a dimer and not a monomer for two reasons. First, the
EIMS exhibits a peak for M+ at m/z 910. Second, there
is no terminal C-H stretch observed in the IR spectrum.
The reactivity of 1 toward internal alkynes did not
result in clean products. Treatment of 1 with DMAD
(dimethyl acetylenedicarboxylate) results in decomposi-
tion to multiple products. Diphenylacetylene does not
react with 1.
While the aforementioned reactions may be thought
of as proceeding by protonation of the hydroxo moiety,
this is not the only mode of reactivity available to the
hydroxoruthenium complex 1. The addition of Ph3SnH,
which does not contain an acidic hydrogen, to 1 affords
the stannyl hydride complex 20 in 32% yield (eq 3). Both
diffractometer
T (°C)
Enraf-Nonius CAD-4
-108.0
radiation
Mo KR (λ ) 0.710 73 Å)
3.0°
60 mm
RuP4O2C20H40
537.5
takeoff angle
cryst-to-detec dist
empirical formula
fw
cryst color, habitat
cryst size (mm)
space group
unit cell dimens
orange blocks
0.25 × 0.30 × 0.30
P212121 (No. 19)
a ) 11.926(2) Å
b ) 12.832 (2) Å
c ) 17.159(4) Å
2626.0(17) Å3, 4
1.36 g/cm3
8.4 cm-1
V, Z
Dcalc
µcalc
scan type
scan rate
2θmax
ω (0.3°/frame)
10.0 s/frame
60.0°
no. of rflns collected
no. of unique rflns
no. of obsd rflns, I > 3.00σ(I)
no. of variables
4219
4191
2710
244
R
0.039
Rw
0.040
goodness of fit
1.32
p factor
0.03
max shift/error in final cycle
max and min peaks in final diff map
<0.05
0.67/-0.20 e Å-3
Sn-P (2J P-Sn ) 174.6 Hz) and Sn-H (2J H-Sn ) 216.1
Hz) couplings are observed by NMR spectroscopy.
Additionally, 1 reacts with dihydrogen to afford dihy-
dride complex 4 (88% yield).
C-H a n d C-C Bon d Activa tion . Tr ea tm en t of
(DMP E)2Ru (H)(OH) w ith Ca r bon yl Com p ou n d s.
An unusual reaction is observed when 1 is treated with
1 equiv of p-tolualdehyde (eq 4). The hydroxo oxygen
F igu r e 1. ORTEP diagram of (DMPE)2Ru(H)(OC(O)C6H4-
Me) (21).
refined using standard least-squares and Fourier tech-
niques. Crystal and data collection parameters are
shown in Table 1, and details of the structure determi-
nation are given in the Experimental section. Positional
and thermal parameters are given as Supporting In-
formation. An ORTEP diagram of 21 is shown in Figure
1. Table 2 provides intramolecular bond lengths and
angles for this compound. The structure confirms the
connectivity assigned to 21. There is no apparent
interaction between the carbonyl oxygen and the ru-
thenium center in the solid state, since the Ru‚‚‚O(2)
distance of 3.43 Å is 1.2 Å longer than Ru-O(1).
is retained, the aldehydic C-H bond is broken, and the
ruthenium carboxylate complex 21 is obtained in 28%
yield.36
Retention of the hydroxo oxygen was confirmed by 17
O
labeling. When 17O-labeled 1 is treated with p-tolual-
dehyde, the oxygen label is retained and 17O NMR shifts
of the product 21 appear at δ 6.7 and -10.35 ppm. It
is likely that the carboxylate ligand in 21 is labile and
that the oxygens scramble intramolecularly in solution
to incorporate the oxygen label into both positions. The
structure of 21 was confirmed by X-ray crystallogra-
phy.47 The structure was solved by direct methods and
(47) Perutz and co-workers have recently solved the X-ray structure
of the related complex (DMPE)2Ru(H)(OCOH): Whittlesey, M. K.;
Perutz, R. N.; Moore, M. H. Organometallics 1996, 15, 5166.
(46) Field, L. D.; George, A. V.; Hockless, D. C. R.; Purches, G. R.;
White, A. H. J . Chem. Soc., Dalton Trans. 1996, 2011.

Monomeric Hydroxoruthenium Complexes
Organometallics, Vol. 17, No. 23, 1998 5077
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for 21
Sch em e 7
Ru-P1
Ru-P2
Ru-P3
Ru-P4
2.308(4)
2.277(4)
2.297(3)
2.294(4)
Ru-O1
O1-C1
C1-O2
Ru‚‚‚O2
2.256(4)
1.256(7)
1.244(8)
3.434(5)
P1-Ru-P2
P1-Ru-P3
P1-Ru-P4
P2-Ru-P3
P2-Ru-P4
P3-Ru-P4
O1-C1-O2
84.19(6)
174.05(15)
95.44(14)
95.52(13)
176.40(14)
84.47(5)
P1-Ru-O1
P2-Ru-O1
P3-Ru-O1
P4-Ru-O1
Ru-O1-C1
O2-C1-C2
O1-C1-C2
87.93(23)
84.34(21)
97.96(22)
99.23(21)
127.5(4)
117.6(6)
116.7(5)
125.1(5)
Sch em e 6
supported the absence of a large detectable anion.
Complex 25 has been characterized further by elemental
analysis and IR spectroscopy. The presence of a stretch
at 1950 cm-1 indicates the presence of a terminal CO
ligand. The identification of this band was confirmed
by the use of 13CO. The labeled product exhibits an IR
stretch at 1915 cm-1, and the stretch at 1950 cm-1 was
no longer present. Surprisingly, another stretch ob-
served in the spectrum of the unlabeled complex 25 at
1628 cm-1 moved to 1604 cm-1 upon 13CO labeling. This
indicates that two CO-containing species are present in
the solid state, one a terminal metal carbonyl and the
other a carboxy (RuCO2H) carbonyl. Further, when the
supernatant from the reaction is concentrated, (DMPE)2-
Ru(H)2 (4) is isolated (7%). It is likely that the dihydride
4 results from â-hydride elimination from 25b before it
precipitates out of solution. Cation 25 may be depro-
tonated with LiN(SiMe3)2 in THF to form the neutral
carbonyl complex (DMPE)2Ru(CO) (26; Scheme 7).48
When the reaction is followed by 1H NMR spectroscopy,
the formation of 1 equiv of HN(SiMe3)2 is observed as
well. The remaining insoluble white powder is pre-
sumed to be LiOH.
We have found that 4 and p-toluic acid also form
complex 21 with loss of dihydrogen. When 1 is treated
with hexafluoroacetone, another carboxylate complex
(22) is formed in 55% yield (eq 4).36 In this case, the
C-C bond is broken and the release of trifluoromethane
is observed by NMR spectroscopy. The 19F{1H} NMR
spectrum contains a singlet at δ -74.4 ppm, consistent
with the presence of a CF3 group in the product 22. The
hydride resonates at δ - 23.40 ppm in the 1H NMR
spectrum, confirming a trans geometry and indicating
that the hydride is located trans to an oxygen-based
ligand. The carbonyl carbon appears as a quartet at δ
161.2 ppm, and the C-F coupling constant (J CF ) 32.8
Hz) is typical for two-bond coupling.
Ha logen for Hyd r id e Exch a n ge a t Ru th en iu m .
Hydroxide 1 is sensitive toward ligand exchange with
halogens. When 1 is dissolved in chlorinated solvents
such as CCl4, CHCl3, and CH2Cl2, varying amounts of
(DMPE)2Ru(H)(Cl),(DMPE)2Ru(OH)(Cl),and (DMPE)2Ru-
Cl2 are observed. Treatment of 1 with 2-iodoethanol in
benzene yields the hydrido iodide complex 2749 in 57%
yield (eq 5). Inequivalent DMPE Me resonances at δ
Ad d ition of Eth ylen e to (DMP E)2Ru (H)(OH).
Much of the observed reactivity of 1 can be rationalized
using the assumption that the first step involves revers-
ible formation of a metal cation/OH- ion pair (23).
Attempts to trap the cation with ethylene resulted in
formation of the ruthenium ethylene complex (DMPE)2-
Ru(C2H4) (2) at 105 °C (Scheme 6). No reaction was
observed at temperatures below 90 °C, and no interme-
diates were observed; however, there is strong evidence
that 2 forms via the cationic hydridoruthenium ethylene
complex 24. This is provided by the reverse of the
synthesis of 1 described earlier, which involves oxidative
addition of water to ethylene complex 2, the mechanism
of which is described in the Discussion (vide supra).28
Syn th esis a n d Rea ctivity of a Ca tion ic Ru th e-
n iu m Hyd r id o Ca r bon yl Com p lex. The proposed
metal cation/OH- ion pair 23 can indeed be trapped
with CO. When a solution of 1 in C6H6 or THF is
exposed to 1 atm of CO at room temperature, a white
precipitate (25, 93%) is formed (Scheme 7). The product
25 is insoluble in common organic solvents, and chlo-
rinated solvents decompose it. FAB-MS clearly shows
the hydrido carbonyl cation. Negative ion FAB-MS
1
1.69 and 1.12 ppm in the H NMR and a singlet at δ
38.6 ppm in the 31P{1H} NMR spectrum are consistent
with its formulation as the trans isomer 27. The
(48) J ones, W. D.; Libertini, E. Inorg. Chem. 1986, 25, 1794.
(49) This complex was originally characterized by IR and elemental
analysis. We further characterized it by NMR spectroscopy. See: Chatt,
J .; Hayter, R. G. J . Chem. Soc. 1961, 2605.

5078 Organometallics, Vol. 17, No. 23, 1998
Kaplan and Bergman
Sch em e 8
Sch em e 9
hydride resonance at δ -18.41 ppm falls into the region
typically observed for hydrides located trans to halide
ligands.
Discu ssion
with alkali-metal alkoxide, amide, thiolate, etc. re-
agents.52 Alternatively, earlier work in these labora-
tories has shown that (DMPE)2Ru(C2H4) (2) is a useful
precursor for a variety of complexes containing metal-
heteroatom bonds. Complex 2 has been treated with
HX (X ) SAr, OAr, PPhH, NHPh) to give the corre-
sponding (DMPE)2Ru(H)(X) complexes via a protonation
mechanism (Scheme 1).35 In contrast to the high
temperatures required to form complexes containing
metal-heteroatom bonds from 2, the hydroxidoruthe-
nium complex 1 undergoes exchange reactions with
thiols, phenols, and silanols at room temperature
(Scheme 1).
Similar to the exchange reactions with silanols, 1
reacts with silica to form 14, containing a Ru-O-silica
linkage. Characterization of supported metal complexes
has been a challenge.53 Physical methods such as IR
and NMR spectroscopy and EXAFS have been em-
ployed54 but have not always provided conclusive char-
acterization. Basset and co-workers have studied the
chemistry of allylrhodium complexes grafted onto silica,
as well as titania and alumina.42 A large part of these
studies has focused on the reactivity of the supported
complexes toward small organic compounds and iden-
tifying the organic products. By probing the reactivity
of the bound complexes, they obtain circumstantial
evidence for the structure of the organometallic groups
on the surface. In contrast, we have developed a differ-
ent method for characterizing silica-bound metal com-
plexes.43 For example, the ruthenium fragment of 14
may be removed from the silica surface as the thiocre-
solate derivative 10, by treating 14 with p-thiocresol
(Scheme 4). By removal of the intact metal complex,
evidence is provided that significant structural changes
F or m a tion of Hyd r oxor u th en iu m Com p lexes
w ith N2O. As mentioned in the Results, we have found
that treatment of (DMPE)2Ru(H)2 (4) with 1 equiv of
N2O affords the hydrido hydroxo complex 1 and that
the dihydroxo complex 5 is formed upon exposure to
excess N2O (eq 1). While N2O proves to be a convenient
anhydrous reagent for inserting an O atom into a
metal-hydride bond under mild conditions, not much
is known about the actual mechanism of N2O-mediated
oxygen atom insertion. This is due in part to the fact
that the use of N2O to directly oxidize organic fragments
on metal centers is rare. As mentioned earlier, Hill-
house and co-workers did show that N2O can be used
to insert oxygen atoms into nickel-carbon and the
relatively oxophilic (group 4) early-metal-hydrogen
bonds.30-34 In the case of Ni (Scheme 8), the authors
invoke coordination of N2O to form a five-coordinate
intermediate prior to N2 loss and oxygen atom trans-
fer.31 They observe no intermediate in this reaction;
however, an intermediate is observed in the Zr system
they studied (Scheme 8). In this case, N2O inserts into
a metal-carbon bond to form a Zr-N linkage before
losing N2 to form the O-inserted product. At present,
the only metal complex reported to contain N2O as a
ligand is [Ru(NH3)5N2O]2+ 50
Because of the instability
.
of this ion, the complex could not be structurally
characterized; however, theoretical studies by Hoffmann
and co-workers indicate that N-linkage complexes are
more stable than the analogous O-linkage complexes.51
In our studies of the N2O-mediated oxygen atom inser-
tion into ruthenium hydride complexes, no intermedi-
ates are observed, yet it seems likely that N2O coordi-
nates initially to the ruthenium center (either via O or
N with subsequent rearrangement) prior to N2 loss with
hydride migration to oxygen (Scheme 9). We cannot
rule out an N2O insertion pathway, however.
(52) Recent examples include: (a) Newman, L. J .; Bergman, R. G.
J . Am. Chem. Soc. 1985, 107, 5314. (b) Fornies, T.; Green, M.; Spencer,
J . L.; Stone, F. G. A. J . Chem. Soc., Dalton Trans. 1977, 1006. (c)
Cowan, R. L.; Trogler, W. C. J . Am. Chem. Soc. 1986, 108, 6387. (d)
Hartwig, J . F.; Anderson, R. A.; Bergman, R. G. Organometallics 1991,
10, 1875. (e) Bohle, D. S.; J ones, T. C.; Rickard, C. E. F.; Roper, W. R.
J . Chem. Soc., Chem. Commun. 1984, 865. (f) Edwards, A. J .; Elipe,
S.; Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Valero, C. Organome-
tallics 1997, 16, 3828.
Tr ea tm en t of th e Hyd r oxor u th en iu m Com p lex
1 w ith P r otic Rea gen ts. The synthesis of compounds
containing late-metal-heteroatom bonds has typically
involved metathesis reactions of metal halide complexes
(50) (a) Armor, J . N.; Taube, H. J . Am. Chem. Soc. 1969, 91, 6874.
(b) Bottomley, F.; Crawford, J . R. J . Chem. Soc. D 1971, 200. (c)
Bottomley, F.; Crawford, J . R. J . Am. Chem. Soc. 1972, 94, 9092. (d)
Diamantis, A. A.; Sparrow, G. J . J . Chem. Soc. D 1970, 819. (e)
Diamantis, A. A.; Sparrow, G. J .; Snow, M. R.; Norman, T. R. Aust. J .
Chem. 1975, 28, 1231.
(53) Roberto, D.; Cariati, E.; Pizzotti, M.; Psaro, R. J . Mol. Catal. A
1996, 111, 97.
(54) See, for example, a discussion of a supported rhodium cata-
lyst: (a) Schwartz, J . Acc. Chem. Res. 1985, 18, 302. (b) Foley, H. C.;
DeCanio, S. J . T.; Chao, K. J .; Onuferko, J . H.; Dybowski, C.; Gates,
B. C. J . Am. Chem. Soc. 1983, 105, 3074. (c) Dufour, P.; Santini, C. C.;
Houtman, C.; Basset, J . M. J . Mol. Catal. 1991, 66, L23.
(51) Tuan, D. F.-T.; Hoffmann, R. Inorg. Chem. 1985, 24, 871.

Monomeric Hydroxoruthenium Complexes
Organometallics, Vol. 17, No. 23, 1998 5079
Sch em e 10
did not occur in the bound complex while on the silica
surface.
As noted above, much of the observed reactivity of 1
can be rationalized using the assumption that the first
step involves reversible formation of a metal cation/OH-
ion pair (23). This is most easily applied to the reaction
of 1 with weak protic acids H-X, perhaps including
alkynes and acetone. In the reaction of triphenyltin
hydride, we suggest that, after OH- dissociation, the
Sn-H bond oxidatively adds to the cationic ruthenium
center in intermediate 23, and then hydroxide removes
a proton from the Ru in 2866 to arrive at the observed
product 20 (Scheme 10). Similar reactivity of 1 toward
H2 would give the cationic dihydrogen hydride complex
[(DMPE)2Ru(H2)(H)][OH] (29), which, upon loss of
water, would form the observed dihydride 4 (Scheme
10). Field and co-workers have shown that dihydrogen
hydride complexes in this system are indeed stable and
may be formed by protonation of 4 by simple alcohols.
In fact, when 4 is dissolved in neat methanol, the
corresponding dihydrogen hydride complex is formed
reversibly and is able to reversibly lose hydrogen to form
the five-coordinate cation (DMPE)2RuH+.39 We believe
we are observing the reverse of this reaction with H2O.
C-H a n d C-C Bon d Act iva t ion of Ca r b on yl
Com p ou n d s. Initial ion pair formation can also be
used to rationalize the apparent oxidations of p-tolual-
dehyde and hexafluoroacetone to the corresponding
carboxylate complexes. O-Coordination of the aldehyde
to the ruthenium center and subsequent hydroxide
attack at the carbonyl carbon in 30 would form the
metallaacetal species 31 (Scheme 11).67 This species is
likely to be unstable with respect to â-elimination,
leading to the dihydride complex 4 and the carboxylic
C-H Activa tion of Ca r bon Acid s. We were inter-
ested in the extent to which hydroxidoruthenium com-
plex 1 may act as a base, in particular to explore its
ability to activate C-H bonds. When treated with
acetone, 1 forms the C-bound enolate complex 15
(Scheme 5). Current interest in transition-metal eno-
late complexes comes from their possible application as
synthons for carbanions, for example in the design of
catalysts for the aldol reaction.55 Enolates have been
shown to bind to metal centers in an η1-mode through
the oxygen atom, or methylene group, or in an η3-mode
as an oxaallyl. Typically, late-metal enolates are C-
bound, although a few examples of late-transition-metal
O-bound enolates have been reported.37,38,56 Hartwig
et al. have found that the enolate ligand tends to bind
through the oxygen atom rather than the methylene in
the related tetrakis(trimethylphosphine)ruthenium sys-
tem.57
Complex 1 also activates the C-H bonds of terminal
alkynes. Monomeric terminal acetylide complexes 16
and 17 are formed when 1 is treated with the corre-
sponding alkyne (Scheme 5). Similarly, when dihydroxo
complex 5 is treated with 2 equiv of phenylacetylene,
the bis(acetylide) complex (18) is obtained (eq 2). The
dimeric species 19 (Scheme 5) is obtained when 1 is
treated with 1,7-octadiyne. Extension of this reactivity
to conjugated alkynes could be a possible approach to
conjugated organometallic systems, which have at-
tracted much recent attention.58-65
(55) (a) Mukaiyama, T.; Banno, K.; Narasaka, K. J . Am. Chem. Soc.
1974, 96, 7503. (b) Yamamoto, Y.; Naruyama, K. Tetrahedron Lett.
1980, 4607. (c) Stille, J . R.; Grubbs, R. H. J . Am. Chem. Soc. 1983,
105, 1665. (d) Evans, D. A.; McGee, L. R. Tetrahedron Lett. 1980, 3975.
(e) Reetz, M. T.; Vougioukas, A. E. Tetrahedron Lett. 1987, 28, 793. (f)
Sato, S.; Matsuda, I.; Izumi, Y. Tetrahedron Lett. 1986, 5517.
(56) Slough, G. A.; Bergman, R. G.; Heathcock, C. H. J . Am. Chem.
Soc. 1989, 111, 938.
(57) Hartwig, J . F.; Andersen, R. A.; Bergman, R. G. J . Am. Chem.
Soc. 1990, 112, 5670.
(58) Yam, V. W.-W.; Lau, V. C.-Y.; Cheung, K.-K. Organometallics
1996, 15, 1740.
(61) Khan, M. S.; Kakkar, A. K.; Ingham, S. L.; Raithby, P. R.; Lewis,
J . J . Organomet. Chem. 1994, 472, 247.
(62) Atherton, Z.; Faulkner, C. W.; Ingham, S. L.; Kakkar, A. K.;
Khan, M. S.; Lewis, J .; Long, N. J .; Raithby, P. R. J . Organomet. Chem.
1993, 462, 265.
(63) Faulkner, C. W.; Ingham, S. L.; Khan, M. S.; Lewis, J .; Long,
N. J .; Raithby, P. R. J . Organomet. Chem. 1994, 482, 139.
(64) Sponsler, M. B. Organometallics 1995, 14, 1920.
(65) Xia, H. P.; J ia, G. Organometallics 1997, 16, 1.
(66) It is also possible that this intermediate could involve a three-
centered bond where the Sn-H bond has not been broken.
(67) An alternate mechanism in which the first step is nucleophilic
attack of the ruthenium-bound hydroxo ligand on the aldehyde is also
possible. This initial step would give an intermediate differing from
32 only in a proton transfer.
(59) Weng, W.; Bartik, T.; Brady, M.; Bartik, B.; Ramsden, J . A.;
Arif, A. M.; Gladysz, J . A. J . Am. Chem. Soc. 1995, 117, 11922.
(60) Narvor, N. L.; Toupet, L.; Lapinte, C. J . Am. Chem. Soc. 1995,
117, 7129.

5080 Organometallics, Vol. 17, No. 23, 1998
Kaplan and Bergman
Sch em e 11
acid, which quickly react to give 21 (vide supra).68
Hexafluoroacetone leads to intermediate 32, which
undergoes C-C cleavage followed by proton transfer to
give 22. When the reaction of 1 with hexafluoroacetone
is monitored by H NMR, the formation of 1 equiv of
CF3H is observed.
neous high-temperature systems.71 The studies of
Yoshida and co-workers on mononuclear rhodium phos-
phine complexes have demonstrated the involvement of
hydroxidometal complexes in the catalytic cycle.72 Two
of the key transformations associated with wgs catalysis
are nucleophilic attack by -OH on a cationic metal
carbonyl complex and subsequent loss of CO2 to gener-
ate a metal hydride (eq 6). The formation of 25b and
1
Rever sible Oxid a tive Ad d ition of Wa ter to a Ru -
(0) Cen ter . When the hydroxoruthenium complex 1 is
exposed to an atmosphere of ethylene in benzene at 105
°C for 1 day, the ruthenium ethylene complex 2 is
formed (Scheme 6). There is strong evidence that the
reverse reaction (treatment of 2 with an excess of water
at elevated temperatures to form the hydroxoruthenium
complex 1) proceeds via cationic hydridoruthenium
ethylene complex 24, which loses ethylene and forms 2
by anion addition.69 We believe that we are observing
the microscopic reverse of this process: dissociation of
hydroxide, coordination of ethylene, and deprotonation
of the metal center to afford the observed product 2.
Tr a p p in g th e Ca tion ic Hyd r id or u th en iu m Com -
p lex w ith CO. If the hydroxo ligand is labile, it should
be possible to trap the resulting [(DMPE)2Ru(H)]+
cation. When 1 is treated with CO at room tempera-
ture, the proposed cation [(DMPE)2Ru(H)]+ formed from
hydroxide dissociation is indeed trapped to form the
hydrido carbonyl complex 25 (Scheme 7). As described
previously, attack of the dissociated -OH on the coor-
dinated carbonyl ligand and â-hydride elimination are
also observed. The attack of hydroxide on the cationic
metal carbonyl complex is noteworthy, as it pertains to
the water gas shift (wgs) reaction. The wgs reaction is
industrially important, as it is used to increase the H2/
CO ratio in synthesis gas.70,71 Currently, this process
is based upon late-metal oxide catalysts in heteroge-
dihydride 4 indicates we are observing examples of both
of these steps.
Con clu sion s
We have found that N2O is capable of mediating
oxygen atom insertion into a late-metal-hydrogen bond
to afford hydroxoruthenium complexes 1 and 5. The
hydroxo ligand is reactive; therefore, additional com-
plexes containing ruthenium-heteroatom bonds (thi-
olates, siloxides, alkoxides) are accessible via exchange
reactions with 1, introducing a mild, general route into
this class of molecules containing late-metal heteroatom
bonds. This exchange chemistry has been extended to
designing experiments employing silica as a ligand. We
have successfully prepared a ruthenium-bound silica
complex and have exploited the exchange reactivity of
the complex to provide strong evidence for its structural
identity. It has become clear that silica can be treated
as a simple3 ligand in both Ir and Ru systems and would
be particularly useful if utilized in catalytic systems.
(70) Storch, H.; Golumbic, N.; Anderson, R. B. The Fischer-Tropsch
and Related Syntheses; Wiley: New York, 1951.
(71) Catalyst Handbook, Springer-Verlag: West Berlin, 1970; Chap-
ters 5 and 6.
(72) Yoshida, T.; Okano, T.; Ueda, Y.; Otsuka, S. J . Am. Chem. Soc.
1981, 103, 3411 and references therein.
(68) When they are followed by NMR spectrometry, the reactions
of both 1 with toluic acid and 4 with toluic acid occur immediately on
mixing.
(69) Characterization of an analogous intermediate may be found
in ref 35.

Monomeric Hydroxoruthenium Complexes
Organometallics, Vol. 17, No. 23, 1998 5081
a minimal amount of toluene (10 mL) and layered with
pentane (40 mL). After 1 day at 25 °C, the tan solution was
decanted from a dark brown residue and the solution was
cooled to -35 °C for 2 day. The tan crystals obtained were
washed with pentane (3 × 1 mL) and dried in vacuo to afford
980 mg (41% yield) of 1. 1H NMR (C6D6): δ 1.52 (m, 4 H, CH2),
1.37 (s, 12 H, P-CH3), 1.34 (m, 4 H, P-CH2), 1.26 (s, 12 H,
P-CH3), -5.40 (br, 1 H, Ru-OH), -20.27 (qn, J HP ) 20.8, 1
H, Ru-H). 31P{1H} NMR δ 46.9 (s). Lit.28 1H NMR (C6D6): δ
1.51 (m, 4 H, CH2), 1.37 (s, 12 H, P-CH3), 1.33 (m, 4 H,
P-CH2), 1.26 (s, 12 H, P-CH3), -5.41 (br, 1 H, Ru-OH),
-20.27 (qn, J HP ) 20.8, 1 H, Ru-H). 31P{1H} NMR: δ 46.8
(s).
tr a n s-(DMP E)2Ru (OH)2 (5) (Meth od A). An 800-mL
bomb was charged with a stir bar and a solution of 1 (1.28 g,
3.06 mmol) in C6H6 (100 mL). The bomb was degassed via
three freeze-pump-thaw cycles, and N2O (1 atm) was con-
densed into the bomb. The solution was warmed to 25 °C and
stirred for 3 days. The resulting brown solution was concen-
trated in vacuo to a dark brown residue, which was dissolved
in minimal toluene (10 mL) and layered with pentane (40 mL).
After 1 day at 25 °C, the tan solution was decanted from a
dark brown residue and the solution was cooled to -35 °C for
2 days. The tan crystals obtained were washed with pentane
(3 × 1 mL) and dried in vacuo to afford 400 mg (30% yield) of
5. 1H NMR (C6D6): δ 1.55 (m, 8 H, P-CH2), 1.27 (s, 24 H,
P-CH3), -7.00 (br, 2 H, OH). 31P{1H} NMR (C6D6): δ 44.6
(s). 13C{1H} NMR (C6D6): δ 29.2 (qn, J CP ) 13.1 Hz, P-CH2),
11.3 (qn, J CP ) 5.9 Hz, P-CH3). IR (Nujol): 3400-3100 (m,
br), 1462 (s), 1423 (s), 1377 (m), 1292 (m), 1277 (m), 1184 (w),
1161 (w), 1082 (w), 941 (s), 912 (s), 889 (s), 835 (m), 796 (m),
733 (m), 700 (m), 642 (m), 515 (m), 503 (m), 492 (m), 484 (m),
441 (m), 424 (m), 409 (w) cm-1. MS-EI: m/z 435 [M+]. HRMS
(EI): m/z calcd for C12H34O2P4Ru 436.0553, obsd 436.0552.
Repeated crystallizations afforded 4 in 95% purity; analytically
pure material could not be obtained.
Complex 1 has been shown to activate C-H, Sn-H, and
C-C bonds under mild conditions, partially due to the
lability and high basicity of the hydroxo ligand. Support
for reactivity of 1 involving hydroxide dissociation is
found in the reactions of ethylene, H2, and particularly
CO. In the last case, the five-coordinate cation resulting
from OH dissociation is trapped by the entering CO
molecule.
Exp er im en ta l Section
Gen er a l Meth od s. Unless otherwise noted, all reactions
and manipulations were carried out in dry glassware under a
nitrogen or argon atmosphere at 20 °C in a Vacuum Atmo-
spheres 553-2 drybox equipped with a MO-40-2 inert-gas
purifier or using standard Schlenk techniques. The amount
of O2 in the drybox atmosphere was monitored with a Teledyne
model #316 trace oxygen analyzer. Glass reaction vessels
fitted with ground-glass joints and Kontes Teflon stopcocks
are referred to as bombs. The other instrumentation and
general procedures used have been described previously.73
NMR Sp ectr oscop y. Solution NMR experiments were
performed on a Bruker AMX spectrometer resonating at 400.13
MHz for 1H, 161.98 MHz for 31P, and 100.61 MHz for 13C that
was equipped with a QNP probe. All solid-state NMR spectra
were acquired on a Chemagnetics CMX-360 NMR spectrom-
eter, using magic angle spinning (5 kHz for carbon, 4-4.5 kHz
for phosphorus) and proton decoupling. A pulse length of 5
µs and a delay of 1 s between scans were used. It was checked
that this was sufficient to allow for complete relaxation of the
observed nuclei by recording spectra with various delays.
Carbon spectra were obtained at 90 MHz, phosphorus at 145.7
MHz, and oxygen at 48.8 MHz. Phosphorus chemical shifts
are given with respect to 85% H3PO4 by using KH2PO4 as an
external standard (3.88 ppm). Carbon chemical shifts are
given with respect to TMS by using hexamethylbenzene as an
external standard (17.3 ppm).
Unless otherwise specified, all reagents were purchased
from commercial suppliers and used without further purifica-
tion. Dimethoxybenzene and phenols were sublimed prior to
use. p-Nitrophenol was recrystallized from C6H6. p-Tolual-
dehyde was distilled from CaSO4. Water and tert-butyldi-
methylsilanol were degassed with three freeze-pump-thaw
cycles. Liquid terminal alkynes and acetone were distilled
from MgSO4 and stored over 4 Å molecular sieves. Acetylene
gas was purified by passage through two -78 °C traps
separated by a concentrated H2SO4 trap. Amine oxides were
purified according to the method of Soderquist and sublimed
before use. Degussa 300 silica was dried in vacuo at 200 °C
for 48 h. Solutions containing silica were agitated by attaching
the reaction vessels to a Kugelrohr motor. cis-(DMPE)2RuCl2,75
trans-(DMPE)2RuCl2,75 (DMPE)2Ru(C2H4),28 (DMPE)2Ru(Et)-
(SC6H4CH3),28 and (DMPE)2Ru(H)(p-SC6H4Me)28 were pre-
pared by literature methods. An improved preparative method
for (DMPE)2Ru(H)2 (4) has been used which involves Na
reduction of (DMPE)2RuCl2 in the presence of 1 atm of H2 and
affords 4 in >95% yield.75
tr a n s-(DMP E)2Ru (OH)2 (5) (Meth od B). An 800-mL
bomb was charged with a stir bar and a solution of 4 (500 mg,
1.24 mmol) in C6H6 (80 mL). The bomb was degassed via three
freeze-pump-thaw cycles, and N2O (1 atm) was condensed
into the bomb. The solution was warmed to 25 °C and stirred
for 3 days. The resulting brown solution was concentrated in
vacuo to a dark brown residue which was dissolved in minimal
toluene (10 mL) and layered with pentane (40 mL). After 1
day at 25 °C, the tan solution was decanted from a dark brown
residue and the solution was cooled to -35 °C for 2 days. The
tan crystals obtained were washed with pentane (3 × 1 mL)
and dried in vacuo to afford 173 mg (32% yield) of 5.
Spectroscopic data are identical with those obtained from
method A.
tr a n s-(DMP E)2Ru (H)(OC6H5) (6). To a solution of 1 (80.2
mg, 0.191 mmol) in C6H6 (10 mL) was added phenol (20.9 mg,
0.222 mmol). After 1 day at 25 °C, the solution was concen-
trated to a beige powder and this solid was redissolved in
toluene for recrystallization by slow pentane diffusion into the
toluene solution of 16. A second recrystallization afforded 23.6
mg (25% yield) of 16 as white crystals: mp 192 °C dec. 1H
NMR (C6D6): δ 7.35 (t, J HH ) 7.8 Hz, 2 H, m-OC6H5), 6.62 (t,
J HH ) 6.8 Hz, 1 H, p-OC6H5), 6.43 (d, J HH ) 7.6 Hz, 2 H,
o-OC6H5), 1.65 (m, 4 H, P-CH2), 1.30 (s, 12 H, P-CH3), 1.23
(m, 4 H, P-CH2), 1.09 (s, 12 H, P-CH3), -23.3 (qn, J HP ) 21.8
Hz, 1 H, Ru-H). 31P{1H} NMR (C6D6): δ 45.4 (s). 13C{1H}
NMR (C6D6): δ 174.0 (C), 129.1 (CH), 120.5 (CH), 109.5 (CH),
tr a n s-(DMP E)2Ru (OH)(H) (1).28 An 800-mL thick-walled
glass vessel fused to a vacuum stopcock was charged with a
stir bar and a colorless solution of 4 (2.30 g, 5.71 mmol) in
C6H6 (100 mL). The bomb was degassed via three freeze-
pump-thaw cycles, and N2O (6.29 mmol) was condensed in.
The solution was warmed to 25 °C and stirred for 12 h. The
resulting brown solution was concentrated in vacuo to a dark
brown residue and washed with pentane (4 × 5 mL) to remove
any unreacted (DMPE)2Ru(H)2. The residue was dissolved in
31.3 (qn, J CP ) 12.3 Hz, CH2), 22.9 (m, PCH3), 15.5 (qn, J CP
)
5.4 Hz, PCH3). IR (KBr): 3058 (w), 2958 (w), 2897 (m), 1928
(m), 1589 (m, br), 1562 (w, br), 1489 (m), 1479 (m, br), 1421
(w, br), 1290 (m, br), 1279 (m, br), 1164 (w, br), 1124 (w, br),
1101 (w, br), 1072 (w, br), 1020 (w, br), 989 (w, br), 935 (s, br),
910 (m, br), 889 (m), 841 (m), 795 (w), 760 (w), 727 (m), 698
(73) Meyer, K. E.; Walsh, P. J .; Bergman, R. G. J . Am. Chem. Soc.
1995, 117, 3749.
(74) Soderquist, J . A.; Anderson, C. L. Tetrahedron Lett. 1986, 27,
3961.
(75) Chatt, J .; Hayter, R. G. J . Chem. Soc. 1961, 896.
(76) We thank Prof. L. Field for this suggestion.
(m), 644 (m), 523 (w), 459 (w) cm-1
.
MS-EI: m/z 496 [M+].
HRMS (EI): m/z calcd for 18H38OP4Ru 496.0917, obsd
C

5082 Organometallics, Vol. 17, No. 23, 1998
Kaplan and Bergman
496.0924. Anal. Calcd for C18H38OP4Ru: C, 43.64; H, 7.73.
Found: C, 43.99; H, 8.22.
Me), 2.19 (s, 3 H, CH3), 1.67 (m, P-CH2), 1.44 (s, P-CH3),
1.23 (m, P-CH2), 1.12 (s, P-CH3), -18.0 (q, 1 H, J HP ) 22.0).
31P{1H} NMR (C6D6): δ 43.2 (s).
tr a n s-(DMP E)2Ru (H)(OC6H4OMe) (7). To a solution of
1 (92.3 mg, 0.220 mmol) in C6H6 (10 mL) was added p-
methoxyphenol (28.4 mg, 0.228 mmol). After 3 days at 25 °C,
C6H6 and H2O were removed in vacuo to afford 111 mg of 17
(DMP E)2Ru (p-SC6H4Me)2 (11) (Meth od A). To a solution
of (DMPE)2Ru(C2H5)(p-SC6H4CH3) (32.5 mg, 0.0587 mmol) in
THF (5 mL) was added p-thiocresol (8.0 mg, 0.0646 mmol).
After 2 days at room temperature, the solution had turned
from light yellow to peach. The solution was concentrated in
vacuo to a bright orange powder. The 1H and 31P{1H} NMR
spectra of the crude material showed only a 3:1 mixture of
cis- and trans-11. Crude 11 was dissolved in toluene (1 mL)
and placed in a pentane diffusion chamber at 20 °C for 1 day.
The red crystals obtained were washed with pentane (3 × 0.5
mL) and dried in vacuo to afford 19.0 mg (50% yield) of trans-
(96%) as a white powder. 1H NMR (C6D6): δ 7.00 (d, J HH
)
8.8 Hz, 2 H, Ph), 6.32 (d, J HH ) 8.8 Hz, 2 H, Ph), 3.61 (s, 3 H,
OMe), 1.69 (m, 4 H, P-CH2), 1.32 (s, 12 H, P-CH3), 1.26 (m,
4 H, P-CH2), 1.10 (s, 12 H, P-CH3), -23.2 (qn, J HP ) 21.7
Hz, 1 H, Ru-H). 31P{1H} NMR (C6D6): δ 45.4 (s). 13C{1H}
NMR (C6D6): δ 166.7 (C), 147.6 (C), 119.1 (CH), 115.1 (CH),
56.1 (OCH3), 30.9 (qn, J CP ) 13.3 Hz, P-CH2), 22.7 (m,
P-CH3), 15.1 (qn, J CP ) 5.3 Hz, P-CH3). IR (KBr): 2958 (w),
2933 (w), 2922 (w), 2897 (m), 2829 (w), 2800 (w), 1930 (m),
1496 (m), 1419 (m), 1279 (m), 1228 (m), 1038 (w), 937 (s), 891
11.
1
tr a n s-11: mp 183 °C; H NMR (THF-d8) δ 7.44 (d, J HH
)
(m), 839 (m), 644 (m) cm-1
obtained due to similarity to 6.
.
Elemental analysis was not
8.0, 4 H, o-SC6H4Me), 7.38 (d, J HH ) 8.0; 4 H, m-SC6H4Me),
2.08 (s, 6 H, SC6H4Me), 1.62 (m, P-CH2), 1.35 (s, 24 H, P-Me);
1H NMR (C6D6) δ 7.49 (d, J HH ) 8.0, 4 H, o-SC6H4Me), 6.80 (d,
J HH ) 8.0; 4 H, m-SC6H4Me), 2.09 (s, 6 H, SC6H4Me), 1.36 (s,
24 H, P-Me); 31P{1H} NMR (THF-d8) δ 36.89 (s); 31P{1H} NMR
(C6D6) δ 36.37 (s); 13C{1H} NMR (C6D6) δ 147.3 (C), 136.9 (CH),
132.2 (C), 128.8 (CH), 30.1 (q, J CP ) 12.1, CH2), 21.3 (C6H4CH3),
15.3 (q, J CP ) 7.0, PCH3); IR (KBr) 3070 (w), 3008 (w), 2964
(w), 2906 (m, br), 2863 (w), 2800 (w), 1593 (w), 1481 (m), 1421
(m, br), 1408 (m), 1379 (w), 1294 (m), 1278 (m), 1238 (w), 1211
(w), 1174 (w), 1130 (w), 1101 (w), 1076 (m), 1016 (w), 939 (s,
br), 930 (s, br), 912, (m, br), 891 (m), 837 (m), 818 (m), 806
(m), 796 (m), 729 (m), 704 (m), 644 (m), 627 (w), 501 (m); MS-
EI m/z 648 [M+]. Anal. Calcd for C26H46P4S2Ru: C, 48.21; H,
7.16. Found: C, 48.64; H, 6.85.
tr a n s-(DMP E)2Ru (H)(OSiP h 3) (8). A solution of triphen-
ylsilanol (62.6 mg, 0.226 mmol) in C6H6 (5 mL) was added to
a solution of 1 (91.3 mg, 0.218 mmol) in C6H6 (15 mL). After
16 h, the C6H6 and water were removed in vacuo. Recrystal-
lization from pentane vapor diffusion into a toluene solution
of 18 gave 93.7 mg of 18 (63.4%) as a white powder: mp 144
°C dec. 1H NMR (C6D6): δ 7.88 (m, 6 H, Ph), 7.29 (m, 6 H,
Ph), 7.21(m, 3 H, Ph), 1.64 (m, 4 H, P-CH2), 1.23 (m, 4 H,
P-CH2), 1.20 (s, 12 H, P-CH3), 1.04 (s, 12 H, P-CH3), -24.4
(qn, J HP ) 21.7 Hz, Ru-H). 31P{1H} NMR (C6D6): δ 43.93 (s).
13C{1H} NMR (C6D6): δ 146.5 (C), 136.5 (CH), 127.6 (CH),
127.1 (CH), 31.5 (qn, J CP ) 12.5 Hz, CH2), 23.3 (qn, J CP ) 7.6
Hz, PCH3), 15.9 (qn, J CP ) 5.0 Hz, PCH3). 17O NMR (C6D6):
δ -93. IR (KBr): 3066 (w), 3045 (w), 2964 (w), 2923 (w), 2899
(w), 2802 (w), 1928 (w), 1656 (w, br), 1637 (w, br), 1589 (w,
br), 1543 (w, br), 1524 (w, br), 1508 (w, br), 1483 (w, br), 1427
(m, br), 1294 (w), 1279 (w), 1117 (s, br), 937 (m), 912 (w), 889
(w), 839 (w), 795 (w), 739 (w), 729 (w), 706 (m), 644 (w), 515
(m), 478 (w) cm-1. MS-EI: m/z 678 [M+]. HRMS (EI): m/z
calcd for C30H48OSiP4Ru 678.1468, obsd 678.1468. Elemental
analysis was attempted but resulted in a low percent of carbon,
likely due to the formation of silicon carbides.
cis-11: 1H NMR (THF-d8) δ 7.67 (d, J HH ) 8.0; 4 H, o-SC6H4-
Me), 6.68 (d, J HH ) 8.0; 4 H, m-SC6H4Me), 2.15 (s, 6 H,
SC6H4Me), 1.79 (d, J HP ) 8.6, 6 H, P-Me), 1.26 (d, J HP ) 6.2,
6 H, P-Me), 1.14 (vt, J HP ) 2.6, 6 H, P-Me), 1.03 (vt, J HP
)
3.4, 6 H, P-Me); 1H NMR (C6D6) δ 8.24 (d, J HH ) 8.0; 4 H,
o-SC6H4Me), 6.96 (d, J HH ) 8.0; 4 H, m-SC6H4Me), 2.17 (s, 6
H, SC6H4Me), 1.69 (d, J HP ) 7.8, 6 H, P-Me), 1.24 (t, J HP
)
3.1, 6 H, P-Me), 0.94 (s, 6 H, P-Me), 0.63 (d, J HP ) 5.8, 6 H,
P-Me); 31P{1H} NMR (THF-d8) δ 38.6 (t, J PP ) 22.1), 33.1 (t,
J PP ) 22.1); 31P{1H} NMR (C6D6) δ 37.6 (t, J PP ) 22.1), 33.0 (t,
J PP ) 22.1).
tr a n s-(DMP E)2Ru (H)(OSiMe2tBu ) (9). To a solution of
1 (45.9 mg, 0.0525 mmol) in C6H6 (20 mL) was added a solution
t
(DMP E)2Ru (p-SC6H4Me)2 (11) (Meth od B). To a solution
of trans-(DMPE)2RuCl2 (183 mg, 0.388 mmol) in toluene (25
mL) was added potassium p-thiocresolate (815 mg, 5.02 mmol,
prepared from KH and p-thiocresol in hexanes). The mixture
was heated to 170 °C for 16 days, at which point NMR analysis
showed clean conversion to a 3:1 mixture of cis- and trans-
(DMPE)2Ru(p-SC6H4Me)2 isomers. The reaction mixture was
filtered through Celite, concentrated in vacuo, and recrystal-
lized from toluene layered with pentane to afford 177 mg (70%)
of cis- and trans-11 as a mixture of yellow and red solids.
Spectroscopic data are identical with those obtained from
method A.
(DMP E)2Ru (p-SC6H4Me)2 (11) (Meth od C). To a solution
of 1 (63.8 mg, 0.150 mmol) in benzene (10 mL) was added
HSC6H4Me (41.0 mg, 0.330 mmol). After 1 h at room tem-
perature, the resulting red solution was placed under vacuum
to remove the volatile materials. Recrystallization from
toluene/pentane vapor diffusion afforded 76.8 mg of 11 (79%
yield). Spectroscopic data are identical with those obtained
from method A.
Th er m olysis of tr a n s-(DMP E)2Ru (p-SC6H4Me)2. A so-
lution of trans-11 and p-xylene (integration standard) in C6D6
was degassed with three freeze-pump-thaw cycles, and then
the tube was flame-sealed. The tube was placed in a 105 °C
oil bath for 1 day. A mixture of 3:1 cis- and trans-11 was
observed in the 1H NMR spectrum. The ratio of isomers did
not change upon continued heating for 12 days at 135 °C.
Tr ea tm en t of tr a n s-(DMP E)2Ru (OH)(H) (1) w ith Silica
in C6D6 a n d Su bsequ en t Rea ction s w ith p-Th iocr esol. To
of BuMe2SiOH (14.7 mg, 0.111 mmol) in C6H6 (2 mL). After
1 day at 25 °C, the solution was concentrated to a red-brown
oil in vacuo to remove H2O and the oil was redissolved in C6H6.
After 2 days more, the solution was concentrated and redis-
solved. This solution was concentrated in vacuo, redissolved
in toluene, and placed in a pentane diffusion chamber at 20
1
°C for 4 days to afford 21 mg (37.5%) of 9 as a white solid. H
NMR (C6D6): δ 1.61 (m, 4 H, P-CH2), 1.45 (s, 12 H, P-CH3),
1.29 (m, 4 H, P-CH2), 1.28 (s, 9 H, Si-C(CH3)3), 1.14 (s, 12
H, P-CH3), 0.21 (s, 6 H, Si(CH3)2), -23.6 (qn, J HP ) 21.6 Hz,
1 H, Ru-H). 31P{1H} NMR (C6D6): δ 43.6 (s). 13C{1H} NMR
(C6D6): δ 31.44 (qn, J CP ) 13.6 Hz, P-CH2), 28.4 (SiC(CH3)3),
23.1 (m, P-CH3), 21.5 (SiC(CH3)3), 15.4 (qn, J CP ) 5.0 Hz,
P-CH3), 1.15 (Si(CH3)2). IR (KBr): 2958 (w), 2933 (w), 2922
(w), 2897 (m), 2829 (w), 2800 (w), 1930 (m), 1497 (m), 1419
(m), 1279 (m), 1228 (m), 1038 (w), 937 (s), 891 (m), 839 (m),
795 (w), 729 (m), 702 (m), 683 (w), 644 (m) cm-1. Elemental
analysis was not obtained due to similarity to 8.
(DMP E)2Ru (H)(p-SC6H4Me) (10).35 To a solution of 1
(45.1 mg, 0.108 mmol) in C6H6 (5 mL) was added p-thiocresol
(13.7 mg, 0.110 mmol). After 1 h at room temperature, the
volatile materials were removed in vacuo. Recrystallization
by pentane vapor diffusion into a concentrated toluene solution
afforded 41.5 mg of 10 (73% yield). 1H NMR (C6D6): δ 7.66
(d, J HH ) 7.8, 2 H, SC6H4Me), 6.89 (d, J HH ) 7.8, 2 H, SC6H4-
Me), 2.19 (s, 3 H, CH3), 1.66 (m, P-CH2), 1.44 (s, P-CH3),
1.23 (m, P-CH2), 1.12 (s, P-CH3), -18.1 (q, 1 H, J HP ) 22.0).
31P{1H} NMR (C6D6): δ 43.3 (s). Lit.35 1H NMR (C6D6): δ 7.65
(d, J HH ) 7.9, 2 H, SC6H4Me), 6.88 (d, J HH ) 7.7, 2 H, SC6H4-

Monomeric Hydroxoruthenium Complexes
Organometallics, Vol. 17, No. 23, 1998 5083
a solution of 1 (98 mg, 0.23 mmol) in THF (40 mL) was added
silica (400 mg). The tan solution turned clear, and the silica
turned tan. The reaction mixture was stirred for 4 h at room
temperature. The product 14 was isolated via filtration,
washed with THF (3 × 20 mL), and dried in vacuo. 13C
(CPMAS) NMR: δ 31.1, 21.1, 14.4. 31P (CPMAS) NMR: δ 44.0.
31P (C6D6) NMR: δ 47.0. IR (neat): 2970 (m), 2908 (s), 1967
(w), 1762 (w), 1545 (br, m), 1424 (m), 920 (br, w), 800 (br, w)
successive recrystallizations from pentane at -70 °C: mp 180
°C dec. 1H NMR (C6D6): δ 7.47 (d, J HH ) 6.9 Hz, 2 H, o-C6H5),
7.18 (s, 2 H, m-C6H5), 6.95 (t, J HH ) 7.4 Hz, 1 H, p-C6H5), 1.50
(s, 12 H, P-CH3), 1.51 (m, 4 H, P-CH2), 1.29 (m, 4 H, P-CH2),
1.24 (s, 12 H, P-CH3), -11.95 (qn, J HP ) 20.0 Hz, 1 H, Ru-
H). 31P{1H} NMR (C6D6): δ 45.5 (s). 13C{1H} NMR (C6D6): δ
133.5 (m, Ru-C), 132.5 (Ru-CC), 130.5 (CH), 127.9 (CH),
122.0 (CH), 109.3 (ipso-C), 31.6 (qn, J CP ) 14.1 Hz, P-CH2),
23.7 (qn, J CP ) 7.0 Hz, P-CH3), 17.1 (qn, J CP ) 7.0 Hz,
P-CH3); IR (KBr): 3064 (w), 2960 (w), 2926 (w), 2899 (m),
2058 (s), 1759 (w), 1632 (w), 1591 (m), 1479 (w), 1417 (m), 1290
(w), 1277 (w), 935 (s), 926 (s), 889 (m), 841 (w), 795 (w), 748
(m), 725 (m), 702 (m), 646 (m), 461 (w) cm-1. MS-EI: m/z 503
[(M - 1)+]. Anal. Calcd for C20H38P4Ru: C, 47.71; H, 7.61.
Found: C, 47.50; H, 7.67.
tr a n s-(DMP E)2Ru (H)(CCP h ) (16) (Meth od B). To a
solution of 4 (60.0 mg, 0.149 mmol) in C6H6 (5 mL) was added
dropwise a solution of phenylacetylene (16.7 mg, 0.164 mmol)
in C6H6 (5 mL). The solution turned to peach after 1 h at room
temperature. Lyophilization, followed by recrystallization
from pentane at -50 °C, afforded 33.8 mg of 16 (45% yield).
Spectroscopic data were identical with those obtained from
method A.
cm-1
.
To a suspension of 14 in THF (50 mL) was added p-
thiocresol (28 mg, 0.23 mmol). The solution was stirred for
30 min at room temperature, during which time the solution
turned yellow. The solution was filtered and concentrated in
vacuo to afford (DMPE)2Ru(H)(p-SC6H4CMe) (10) in 95% yield.
Spectroscopic data are consistent with reported values.35
When 14 is treated with excess p-thiocresol under similar
conditions, the bis(thiolate) complex 11 is obtained in 96%
yield. Spectroscopic data are consistent with reported values.39
Tr ea tm en t of (DMP E)2Ru (C2H4) (2) w ith Silica a n d
Su bsequ en t Rea ction s w ith p-Th iocr esol. To a solution
of 2 (100 mg, 0.23 mmol) in THF (55 mL) was added silica
(400 mg). The tan solution turned clear, and the silica turned
tan. The reaction mixture was stirred for 4 h at room
temperature. The product 14 was isolated via filtration,
washed with THF (2 × 15 mL), and dried in vacuo. 13C
(CPMAS) NMR: δ 31.2, 21.8, 15.4. 31P (CPMAS) NMR: δ 43.4.
31P (C6D6) NMR: δ 47.1. IR (neat): 2975 (m), 2910 (s), 1966
(w), 1761 (w), 1540 (br, m), 1423 (m), 920 (br, w), 805 (br, w)
tr a n s-(DMP E)2Ru (H)(CCH) (17). ASchlenk flask equipped
with a stir bar was charged with 1 (94.3 mg, 0.225 mmol) in
C6H6 (10 mL). Acetylene gas was bubbled through the solution
for 25 min at 25 °C. The volatile materials were removed in
vacuo to afford 93 mg of 17 (97% yield) as a white powder.
Recrystallization of 17 from pentane (0.5 mL) at - 50 °C
affords 31 mg of 17 (32% yield) as microcrystalline needles.
1H NMR (C6D6): δ 1.85 (s, 1 H, CCH), 1.56 (s, 12 H, P-CH3),
1.57 (m, 4 H, P-CH2), 1.30 (m, 4 H, P-CH2), 1.24 (s, 12 H,
P-CH3), -12.37 (qn, J HP ) 21.5 Hz, 1 H, Ru-H). 31P{1H}
NMR (C6D6): δ 45.2 (s). 13C{1H} NMR (C6D6): δ 121.8 (qn,
J CP ) 13.7 Hz, Ru-C), 91.2 (Ru-CC), 31.8 (qn, J CP ) 13.8
cm-1
.
To a solution of 14 in THF (50 mL) was added p-thiocresol
(28 mg, 0.23 mmol). The solution was stirred for 30 min at
room temperature, during which time the solution turned
yellow. The solution was filtered and concentrated in vacuo
to afford (DMPE)2Ru(H)(p-SC6H4CMe) (10) in 95% yield.
Spectroscopic data were consistent with reported values.35
When 14 is treated with excess p-thiocresol under similar
conditions, the bis(thiolate) complex 11 is obtained, also in 95%
yield. Spectroscopic data were consistent with reported val-
ues.39
Hz, P-CH2), 24.0 (qn, J CP ) 6.9 Hz, P-CH3), 17.1 (qn, J CP
)
3.9 Hz, P-CH3). IR (KBr): 3269 (m), 2962 (w), 2922 (w), 2899
(m), 1905 (m), 1730 (w), 1421 (w), 1277 (w), 939 (s), 928 (s),
889 (w), 841 (w), 795 (w), 727 (w), 703 (w), 644 (w), 530 (w)
cm-1
.
MS-EI: m/z 427 [M+ - 1]. HRMS (EI) m/z calcd for
tr a n s-(DMP E)2Ru (H)(CH2C(O)CH3) (15). A 50-mL bomb
was charged with a stir bar and a solution of 1 (103.6 mg, 0.247
mmol) in C6H6 (10 mL). The bomb was degassed via three
freeze-pump-thaw cycles, and acetone (0.270 mmol) was
condensed into the bomb. The solution was warmed to 25 °C
and stirred for 2 h. The volatile materials were removed in
vacuo to afford 108 mg (95% yield) of 15. The product was
washed with pentane (3 × 3 mL). Analytically pure 15 (39
mg, 34% yield) was obtained as tan crystals by two successive
recrystallizations using pentane vapor diffusion into a toluene
solution of 15 at 25 °C. 1H NMR (C6D6): δ 2.13 (s, 3 H, C(O)-
CH3), 1.57 (m, 6 H, Ru-CH2 and P-CH2), 1.38 (s, 12 H,
P-CH3), 1.21 (m, 4 H, P-CH2), 1.14 (s, 12 H, P-CH3), -16.67
(qn, J HP ) 22.2 Hz, 1 H, Ru-H). 31P{1H} NMR (C6D6): δ 43.0
(s). 13C{1H} NMR (C6D6): δ 210.7 (C), 31.0 (qn, J CP ) 13.7
Hz, P-CH2), 30.6 (COCH3), 25.7 (qn, J CP ) 7.6 Hz, P-CH3),
18.0 (qn, J CP ) 4.2 Hz, Ru-CH2), 15.2 (qn, J CP ) 5.0 Hz,
P-CH3). IR (KBr): 2958 (m), 2922 (m), 2897 (s), 1928 (s), 1713
(w), 1475 (m), 1444 (m), 1419 (s), 1365 (m), 1288 (w), 1279
(m), 1232 (w), 1074 (w), 991 (w), 935 (s), 889 (s), 862 (w), 840
C14H34P4Ru 428.0655, obsd 428.0657.
tr a n s-(DMP E)2Ru (H)(13C13CH) (17-13C2). In a resealable
NMR tube was added a solution of 1 (8.4 mg, 0.020 mmol) in
C6D6 (0.5 mL). H13C13CH (0.022 mmol) was condensed into
the solution via vacuum-transfer techniques. After 3 h at room
temperature, the volatile materials were removed in vacuo to
afford pure 17-13C2 as a white solid (7.8 mg, 91%). 1H NMR
(C6D6): δ 1.85 (d, J ) 35.0 Hz, 1 H, CCH), 1.56 (s, 12 H,
P-CH3), 1.57 (m, 4 H, P-CH2), 1.30 (m, 4 H, P-CH2), 1.25 (s,
12 H, P-CH3), -12.39 (br, 1 H, Ru-H). 31P{1H} NMR
(C6D6): δ 45.1 (s). 13C{1H} NMR (C6D6): δ 122.3 (dqn, J CP
)
13.7 Hz, J CC ) 100.0 Hz, Ru-C), 121.3 (d, J CC ) 100.0 Hz,
Ru-CC), 31.8 (qn, J CP ) 13.8 Hz, P-CH2), 24.0 (qn, J CP ) 6.9
Hz, P-CH3), 17.1 (qn, J CP ) 3.9 Hz, P-CH3). IR (KBr): 3253
(m), 2962 (w), 2922 (w), 2899 (m), 1838 (s), 1726 (w), 1632 (w),
1421 (w), 1294 (w), 1277 (w), 941 (s), 926 (s), 889 (m), 841 (w),
795 (w), 727 (w), 702 (w), 646 (w), 532 (w) cm-1. MS-EI: m/z
429 [M+ - 1].
tr a n s-(DMP E)2Ru (CCP h )2 (18).46 To a solution of 4 (30.0
mg, 0.0744 mmol) in benzene was added HCCPh (16.7 mg,
0.164 mmol). The reaction mixture was stirred at room
temperature for 10 days, and the volatile materials were
removed in vacuo to afford 18 in 92% yield. 1H NMR (THF-
d8): δ 2.09 (24 H, m, CH3), 2.22 (8 H, br s, CH2), 7.43 (10 H,
m, CH). 31P{1H} NMR (THF-d8): δ 40.6 (s). Lit.46 1H{31P}
NMR (THF-d8): δ 2.08 (24 H, m, CH3), 2.21 (8 H, br s, CH2),
7.43 (10 H, m, CH). 31P{1H} NMR (THF-d8): δ 40.8 (s).
tr a n s-(DMP E)2(H)Ru CC(CH2)4CCRu (H)(DMP E)2 (19).
To a solution of 1 (99 mg, 0.24 mmol) in C6H6 (10 mL) was
added 1,7-octadiyne (34.5 µL, 0.26 mmol). After 16 h, the
solution was concentrated in vacuo to a white powder and
(m), 795 (w), 727 (s), 702 (s), 683 (w), 644 (m), 459 (w) cm-1
.
MS-EI m/z 459 [(M)+]. Anal. Calcd for C15H38OP4Ru: C,
39.21; H, 8.34. Found: C, 39.20; H, 8.32.
tr a n s-(DMP E)2Ru (H)(CCP h ) (16) (Meth od A). To a
solution of 1 (98 mg, 0.23 mmol) in C6H6 (5 mL) was added
dropwise a solution of phenylacetylene (26 mg, 0.26 mmol) in
C6H6 (5 mL). The tan solution turned to peach after 0.5 h at
25 °C. Lyophilization, followed by dissolution of the remaining
solid in pentane, filtration through Celite, and concentration
in vacuo afforded 88 mg (74% yield) of 16 as an orange solid
which was pure by NMR spectroscopy. Analytically pure
yellow needles of 16 (33 mg, 28% yield) were obtained by two

5084 Organometallics, Vol. 17, No. 23, 1998
Kaplan and Bergman
recrystallized from pentane (4 mL) at -50 °C to afford 35 mg
of 19 as colorless microcrystals (33% yield). 1H NMR (C6D6):
δ 2.64 (br, 4 H, CH2CH2), 1.93 (m, 4 H, CH2CH2), 1.62 (s, 24
H, P-CH3), 1.63 (m, 8 H, P-CH2), 1.40 (m, 8 H, P-CH2), 1.35
(s, 24 H, P-CH3), -12.29 (qn, J HP ) 21.3 Hz, 2 H, Ru-H).
31P{1H} NMR (C6D6): δ 45.9 (s). 13C{1H} NMR (C6D6): δ 106.6
(qn, J CP ) 14.4 Hz, RuCC), 104.0 (RuCC), 32.5 (RuCCCH2),
32.0 (qn, J CP ) 13.9 Hz, P-CH2), 24.3 (qn, J CP ) 6.5 Hz,
P-CH3), 22.9 (RuCCCH2CH2), 17.5 (qn, J CP ) 6.3 Hz, P-CH3).
IR (KBr): 2083 (m), 1716 (m), 1419 (m), 1329 (w), 1290 (m),
1275 (m), 1072 (w), 935 (m), 925 (m), 910 (m), 887 (m), 836
727 (w), 702 (w), 646 (w), 418 (w) cm-1. MS-EI: m/z 537 [(M)+].
Anal. Calcd for C20H40O2P4Ru: C, 44.69; H, 7.50. Found: C,
45.06; H, 7.71.
tr a n s-(DMP E)2Ru (H)(OC(O)p-C6H4CH3) (21) (Meth od
B). To a solution of 4 (60 mg, 0.149 mmol) in benzene (8 mL)
was added p-toluic acid (22.3 mg, 0.164 mmol). After 2 h at
room temperature, the solution was concentrated to a peach
solid to afford 76.8 mg of spectroscopically pure 21 (96% yield).
tr a n s-(DMP E)2Ru (H)(17OC(17O)p-C6H4CH3) (21-17O2) was
prepared in an fashion analogous to that for 21 from 1-17O28
and p-tolualdehyde. 1H NMR (C6D6): δ 8.31 (d, J HH ) 8.0 Hz,
2 H, C6H4), 7.10 (d, J HH ) 8.0 Hz, 2 H, C6H4), 2.12 (s, 3 H,
C6H4CH3), 1.99 (m, 4 H, P-CH2), 1.37 (s, 12 H, P-CH3), 1.35
(w), 700 (m), 644 (w), 622 (w), 509 (m), 498 (m), 447 (m) cm-1
;
IR (Nujol): 2960 (w), 2920 (m), 2899 (s), 2850 (w), 2819 (w),
2079 (w), 1732 (s), 1632 (w), 1603 (w), 1421 (w), 1389 (w), 1350
(w), 1292 (w), 1277 (w), 1238 (w), 1193 (w), 1149 (w), 937 (s),
928 (s), 889 (w), 839 (w), 725 (w), 702 (w), 644 (w), 461 (w)
(m, 4 H, P-CH2), 1.15 (s, 12 H, P-CH3), -22.42 (qn, J HP
)
21.3 Hz, 1 H, Ru-H). 31P{1H} NMR (C6D6): δ 46.6 (s). 17O
NMR (C6D6): δ 6.7 (br), -10.4 (br).
cm-1
.
MS-EI: m/z 910 [(M)+]. HRMS (EI): m/z calcd for
X-r a y Cr ysta llogr a p h ic Stu d y of (DMP E)2Ru (H)(OC-
(O)C6H4CH3) (21). Crystals of 21 suitable for X-ray diffrac-
tion were obtained by evaporation of a benzene solution of 21
over 2 weeks. A fragment of one of these orange blocky
crystals having dimensions of 0.25 × 0.30 × 0.30 mm was
mounted on a glass fiber using Paratone N hydrocarbon oil.
All measurements were made on an Enraf-Nonius CAD-4
diffractometer using graphite-monochromated Mo KR radia-
tion. The final cell parameters and specific collection param-
eters are given in Table 1. The 4219 raw intensity data were
converted to structure factor amplitudes by correction for scan
speed, background, and Lorentz and polarization effects.
Space group P212121 was confirmed by successful refinement.
The enantiomorph was determined by parallel refinement of
both the inverse and obverse structures. The structure with
the lower residuals is the one reported. No decay or absorption
correction was applied. The structure was solved by Patterson
methods and refined via standard least-squares and Fourier
techniques. All non-hydrogen atoms were refined anisotropi-
cally, and hydrogen atoms were included with isotropic
thermal parameters but not refined. Five data with small
intensity and Fo values much greater than Fc were removed
from the least-squares refinement. The final residuals for 21
are given in Table 1. Selected bond lengths and angles are
given in Table 2, and an ORTEP diagram is shown in Figure
1. Positional and anisotropic thermal parameters and com-
plete tables of bond distances and angles are provided in the
Supporting Information.
C
32H74P8Ru2 910.1779, obsd 910.1796.
tr a n s-(DMP E)2Ru (H)(Sn P h 3) (20). To a solution of 1 (77
mg, 0.18 mmol) in C6H6 (5 mL) was added dropwise a solution
of triphenylstannane (67 mg, 0.19 mmol) in C6H6 (5 mL) at 25
°C. After 0.5 h, the volatile materials were removed in vacuo
and recrystallization from pentane (4 mL) diffusion into a
concentrated toluene solution (1 mL) afforded 43.3 mg of 20
as white needles (32% yield). 1H NMR (C6D6): δ 7.90 (d, J HH
) 6.9 Hz, 2 H, o-C6H5), 7.23 (t, 2 H, m-C6H5), 7.08 (br, 1 H,
p-C6H5), 1.78 (m, 4 H, P-CH2), 1.24 (s, 12 H, P-CH3), 1.35
(m, 4 H, P-CH2), 1.06 (s, 12 H, P-CH3), -13.14 (qn, J HP
)
22.5 Hz, 1 H, Ru-H). 1H{31P} NMR (C6D6): δ -13.14 (s, J HSn
) 216.1 Hz, Ru-H). 31P{1H} NMR (C6D6): δ 46.3 (s, J PSn
)
174.6 Hz). 13C{1H} NMR (C6D6): δ 158.2 (ipso-C), 138.9 (CH,
J CSn ) 33.8 Hz), 127.5 (CH), 125.9 (CH), 33.1 (qn, J CP ) 13.8
Hz, P-CH2), 28.3 (qn, J CP ) 7.7 Hz, P-CH3), 22.7 (qn, J CP
)
6.7 Hz, P-CH3). IR (KBr): 3043 (w), 2966 (w), 2900 (m), 1869
(m), 1471 (w), 1419 (m), 1389 (w), 1296 (w), 1277 (w), 1059
(w), 935 (s), 903 (m), 889 (m), 854 (w), 839 (m), 723 (s), 702
(s), 679 (w), 652 (w), 638 (m), 465 (w), 453 (w) cm-1
. Anal.
Calcd for C30H48P4RuSn: C, 47.89; H, 6.43. Found: C, 47.52;
H, 6.75.
Tr ea tm en t of 1 w ith H 2. To a bomb containing a solution
of 1 (55 mg, 0.131 mmol) in benzene (10 mL) was added H2 (1
atm) via vacuum-transfer techniques. After 1 day, the volatile
materials were removed in vacuo to afford 46.5 mg of 4 (88%).
1H NMR (C6D6): δ 1.61 (s, 6 H, PCH3), 1.40-1.33 (br m, 8 H,
PCH2), 1.35 (s, 6 H, PCH3), 1.31 (d, 6 H, PCH3), 1.22 (s, 6 H,
PCH3), 1.04 (d, 6 H, PCH3), -9.57 (m, 2 H, Ru-H). 31P{1H}
NMR (C6D6) δ 47.6 (vt, J ) 21.5 Hz), 38.6 (vt, J ) 21.5 Hz).
Lit.55 1H NMR (C6D6): δ 1.01 (d, 6 H, P-CH3), 1.18 (s, 6 H,
P-CH3), 1.30 (d, 6 H, P-CH3), 1.36 (s, 6 H, P-CH3), 1.56 (s,
6 H, P-CH3), 1.33-1.39 (br m, 8 H, P-CH2), -9.60 (m, 2 H,
Ru-H). 31P{1H} NMR (C6D6): δ 38.3 (vt, J ) 21.5 Hz), 47.3
(vt, J ) 21.5 Hz).
tr a n s-(DMP E)2Ru (H)(OC(O)p-C6H4CH3) (21) (Meth od
A). To a solution of 1 (60 mg, 0.14 mmol) in C6H6 (3 mL) was
added dropwise a solution of p-tolualdehyde (19 mg, 0.16
mmol) in C6H6 (3 mL) at 25 °C. After 1.5 h, the solution was
concentrated in vacuo to a peach solid that was spectroscopi-
cally pure (76 mg, 99% yield). X-ray-quality crystals of 21 (22
mg, 28% yield) were obtained by two successive recrystalliza-
tions using pentane vapor diffusion into a toluene solution of
21 at 25 °C: mp 160 °C dec. 1H NMR (C6D6): δ 8.32 (d, J HH
) 8.0 Hz, 2 H, C6H4), 7.10 (d, J HH ) 8.0 Hz, 2 H, C6H4), 2.12
(s, 3 H, C6H4CH3), 1.98 (m, 4 H, P-CH2), 1.37 (s, 12 H,
P-CH3), 1.36 (m, 4 H, P-CH2), 1.15 (s, 12 H, P-CH3), -22.45
(qn, J HP ) 21.3 Hz, 1 H, Ru-H). 31P{1H} NMR (C6D6): δ 46.6
(s); 13C{1H} NMR (C6D6): δ 171.1 (CdO), 138.6 (C), 137.9 (C),
130.5 (CH), 129.0 (CH3), 128.6 (CH), 31.7 (qn, J CP ) 13.6 Hz,
P-CH2), 22.9 (qn, J CP ) 7.3 Hz, P-CH3), 16.0 (qn, J CP ) 5.4
Hz, P-CH3). IR (KBr): 2958 (w), 2895 (w), 1928 (w), 1591
(m), 1549 (s), 1421 (w), 1404 (m), 1387 (w), 1290 (w), 1279 (w),
937 (m), 924 (w), 889 (w), 841 (w), 795 (w), 785 (w), 762 (w),
tr a n s-(DMP E )2R u (H )(OC(O)CF 3) (22). A bomb was
charged with a solution of 1 (93.7 mg, 0.022 mmol) in benzene
(10 mL). CF3C(O)CF3 (0.022 mmol) was condensed into the
solution via vacuum-transfer techniques. After 1 day at room
temperature, the volatile materials were removed in vacuo and
the resulting off-white powder was recrystallized by layering
pentane (3 mL) onto a toluene (12 mL) solution of 22. Yellow
crystals of 22 were obtained in 55% yield (60.9 mg). 1H NMR
(C6D6): δ 1.73 (m, 4 H, P-CH2), 1.28 (s, 12 H, P-CH3), 1.20
(m, 4 H, P-CH2), 1.04 (s, 12 H, P-CH3), -23.40 (qn, J HP
20.9 Hz, 1 H, Ru-H). 31P{1H} NMR (C6D6): δ 45.2 (s). 13C-
{1H} NMR (C6D6): CF3 carbon not observed, δ 161.2 (q, J CF
)
)
32.8 Hz, CO), 30.5 (qn, J CP ) 13.7 Hz, P-CH2), 21.5 (qn, J CP
) 7.0 Hz, P-CH3), 14.6 (qn, J CP ) 5.5 Hz, P-CH3). 19F{1H}
NMR (C6D6): δ -74.4. IR (KBr): 2966 (w), 2902 (m), 1932
(w), 1693 (s), 1682 (s), 1421 (w), 1294 (w), 1279 (w), 1200 (s),
1167 (m), 1122 (m), 937 (s), 912 (w), 891 (m), 839 (m), 833 (w),
795 (w), 729 (m), 704 (m), 644 (w) cm-1. MS-EI m/z 515 [M+].
Anal. Calcd for C14H33F3O2P4Ru: C, 32.63; H, 6.45. Found:
C, 32.85; H, 6.14.
Tr ea tm en t of 1 w ith Eth ylen e. A 100 mL bomb was
charged with a solution of 1 (94.2 mg, 0.225 mmol) in benzene
(20 mL). Ethylene (3 atm) was condensed in via vacuum-
transfer techniques. The solution was heated to 105 °C for
24 h. The volatile materials were removed in vacuo, and the
resulting white solid was extracted with pentane (4 × 20 mL).
Concentration of the pentane extracts afforded 64.2 mg of

Monomeric Hydroxoruthenium Complexes
Organometallics, Vol. 17, No. 23, 1998 5085
spectroscopically pure 2 (67% yield). 1H NMR (C6D6): δ 1.49
(d, J ) 4.2 Hz), 1.35 (m), 1.24 (m), 1.17 (vt, J ) 42.2 Hz), 1.03
(s), 1.02 (m), 0.85 (m), 0.79 (t, J ) 2.3 Hz). 31P{1H} NMR
tr a n s-(DMP E)2Ru (H)(I) (27) (Meth od A).49 To a solution
of 1 (83.0 mg, 0.0949 mmol) in C6H6 (5 mL) was added ICH2-
CH2OH (17.9 mg, 0.104 mmol) in C6H6 (5 mL). After 20 min
at room temperature, the solution was concentrated in vacuo
to a pale yellow solid. Recrystallization from pentane (80 mL)
at -70 °C afforded 57.6 mg of 27 as white needles (57% yield).
1H NMR (C6D6): δ 1.69 (s, 12 H, P-CH3), 1.64 (m, 4 H,
P-CH2), 1.23 (m, 4 H, P-CH2), 1.12 (s, 12 H, P-CH3), -18.41
(qn, J HP ) 21.4 Hz, 1 H, Ru-H). 31P{1H} NMR (C6D6): δ 38.6
(s). 13C{1H} NMR (C6D6): δ 31.2 (qn, J CP ) 13.3 Hz, P-CH2),
23.7 (qn, J CP ) 7.2 Hz, P-CH3), 19.7 (qn, J CP ) 6.2 Hz,
P-CH3). IR (KBr): 2960 (w), 2922 (w), 2897 (m), 1923 (m),
1419 (m), 1290 (w), 1279 (w), 937 (s), 891 (m), 839 (w), 727
(m), 702 (m), 675 (w), 644 (w), 457 (w) cm-1. MS-EI: m/z 529
[M+]. Anal. Calcd for C20H38P4Ru: C, 27.23; H, 6.28.
Found: C, 27.50; H, 6.19.
(C6D6): δ 43.7 (t, J ) 28.5 Hz), 37.0 (t, J ) 28.5 Hz). Lit.35 1
H
NMR (C6D6): δ 1.48 (d, J ) 4.2 Hz), 1.35 (m), 1.22 (m), 1.17
(vt, J ) 42.2 Hz), 1.06 (s), 1.02 (m), 0.85 (m), 0.79 (t, J ) 2.3
Hz). 31P{1H} NMR (C6D6): δ 43.9 (t, J ) 28.6 Hz), 37.2 (t, J
) 28.6 Hz).
tr a n s-[(DMP E)2Ru (H)(CO)][OH] (25a ). A bomb (120 mL)
was charged with a solution of 1 (101 mg, 0.240 mmol) in
benzene (15 mL). The solution was degassed (three freeze-
pump-thaw cycles), and an atmosphere of CO was condensed
in (1 atm) via vacuum-transfer techniques. A white precipitate
formed within 5 min at room temperature. The solution was
stirred for 1 day at room temperature, and the precipitate was
isolated via filtration and washed with THF (3 × 5 mL). IR
(Nujol): 3394 (br), 2669 (w), 2621 (w), 1950 (s), 1670 (m), 1628
(s), 1431 (m), 1379 (s), 1333 (m), 1296 (m), 1286 (m), 1250 (w),
1140 (w), 1084 (w), 976 (m), 949 (m), 941 (m), 903 (m), 849
(m), 837 (w), 804 (w), 741 (m), 715 (m) cm-1. MS-FAB: m/z
431 [M+]. Anal. Calcd for C13H34O2P4Ru: C, 34.90; H, 7.66.
Found: C, 34.72; H, 7.18.
Ack n ow led gm en t. We thank the National Insti-
tutes of Health (Grant No. GM-25459) and the Arthur
C. Cope Fund, administered by the American Chemical
Society, for generous financial support of this work. We
are grateful to Dr. F. J . Hollander, director of the
University of California Berkeley College of Chemistry
X-ray diffraction facility (CHEXRAY), for solving the
crystal structure of 21. We also thank Prof. R. A.
Andersen for suggesting the use of N2O in the synthesis
of 1 and for helpful discussions and Prof. R. N. Perutz
for disclosure of results prior to publication. We thank
the DuPont Co. for partial research support and access
to facilities and are grateful to G. Cres Campbell and
Dr. Emilio Bunel for recording the NMR spectra of 14.
tr a n s-[(DMP E)2Ru (H)(13CO)][OH] (25a -13C) was pre-
pared from 1 and 13CO in a fashion analogous to that used for
25a . IR (Nujol): 3394 (br), 2669 (w), 2621 (w), 1915 (s), 1670
(m), 1604 (s), 1431 (m), 1379 (s), 1333 (m), 1296 (m), 1286 (m),
1250 (w), 1140 (w), 1084 (w), 976 (m), 949 (m), 941 (m), 903
(m), 849 (m), 837 (w), 804 (w), 741 (m), 715 (m) cm-1
.
tr a n s-(DMP E)2Ru (CO) (26).48 To a suspension of 25 (56
mg, 0,13 mmol) in THF (10 mL) was added LiNTMS2 (30 mg,
0.18 mmol). Within 1 h at room temperature, the solution
appeared to be homogeneous. Volatile materials were removed
in vacuo, and the resulting white powder was extracted with
benzene (3 × 5 mL). The benzene extracts were filtered and
concentrated in vacuo to a white solid. 1H NMR (C6D6): δ 1.31
(br). 31P{1H} NMR (C6D6): δ 40.4 (s). IR (KBr): 2953 (w),
2875 (w), 1954 (s), 1927 (sh), 1450 (sh), 1428 (m), 1389 (m),
Su p p or tin g In for m a tion Ava ila ble: Text and tables
giving structural tables for 21 and figures giving CPMAS
spectra of 1 and 14 (14 pages). See any current masthead page
for ordering information and Internet access instructions.
1292 (m), 935 (s), 901 (m), 858 (w), 727 (m) cm-1
.
Lit.48 1H
NMR (C6D6): δ 1.31 (br). IR (KBr): 2958 (w), 2905 (w), 1945
(s), 1925 (sh), 1453 (sh), 1429 (m), 1380 (m), 1300 (m), 942 (s),
910 (m), 860 (w), 724 (m) cm-1
.
OM980295D