Reactivity of [1,2-bis(dimethylphosphanyl)ethane](mesitylidyne)tungsten(IV) hydride with group 7 and 8 transition metal carbonyl complexes

Article abstract of DOI:10.1002/1099-0682(200106)2001:6<1559::aid-ejic1559>3.0.co;2-y

The reaction between the tungsten hydride complex trans-W(CMes)(dmpe)₂H [1, dmpe = 1,2-bis(dimethylphosphanylethane)] and a series of electrophilic transition metal carbonyl compounds has been investigated, to explore the generality of W-H reductions of coordinated CO. Hydride transfer to the mononuclear [Fe(CO)₅], and to the dinuclear [Re₂(CO)₁₀], yields the neutral heterobimetallic formyl complexes trans-W{(μ-OCH)Fe(CO)₄}(CMes)(dmpe)₂ (2) and trans-W{(μ-OCH)Re₂(CO)₉}(CMes)(dmpe)₂ (3a), respectively. In the latter case, after one week at room temperature, 3a is smoothly converted into the stable ionic complex [W(CMes)(CO)(dmpe)₂]⁺[Re₂(CO)₉H] ^- (3b). Reaction with the cluster [Ru₃(CO)₁₂] results in the formation of an unstable formyl complex, which undergoes a direct rearrangement at -20 °C to produce the ionic complex [W(CMes)(CO)(dmpe)₂]⁺[Ru₃(CO) ₁₁H]^- (4) as the final product. The molecular structure of 4 was unambiguously established by single-crystal X-ray diffraction.

Full text of DOI:10.1002/1099-0682(200106)2001:6<1559::aid-ejic1559>3.0.co;2-y

FULL PAPER
Reactivity of [1,2-Bis(dimethylphosphanyl)ethane](mesitylidyne)tungsten(IV)
Hydride with Group 7 and 8 Transition Metal Carbonyl Complexes
Franck Furno,[a] Thomas Fox,[a] Montserrat Alfonso,[a] and Heinz Berke*[a]
Keywords: Hydride complexes / Formyl complexes / Decarbonylation
The reaction between the tungsten hydride complex trans-
W(CMes)(dmpe)2H [1, dmpe = 1,2-bis(dimethylphosphanyle-
thane)] and a series of electrophilic transition metal carbonyl
ter case, after one week at room temperature, 3a is smoothly
converted into the stable ionic complex [W(CMes)(CO)-
(dmpe)2]+[Re2(CO)9H]− (3b). Reaction with the cluster
compounds has been investigated, to explore the generality [Ru3(CO)12] results in the formation of an unstable formyl
of W−H reductions of coordinated CO. Hydride transfer to
the mononuclear [Fe(CO)5], and to the dinuclear [Re2(CO)10],
yields the neutral heterobimetallic formyl complexes trans-
W{(µ-OCH)Fe(CO)4}(CMes)(dmpe)2 (2) and trans-W{(µ-
OCH)Re2(CO)9}(CMes)(dmpe)2 (3a), respectively. In the lat-
complex, which undergoes a direct rearrangement at −20 °C
to produce the ionic complex [W(CMes)(CO)(dmpe)2]+-
[Ru3(CO)11H]− (4) as the final product. The molecular struc-
ture of 4 was unambiguously established by single-crystal X-
ray diffraction.
Introduction
plexes and hydridometal carbonyls are commonly invoked
as reactive intermediates in both catalytic and stoichi-
ometric CO reduction reactions.[13] The synthesis and char-
acterization of formyl-metal complexes remains important
for fuller investigation of the mechanism of
FischerϪTropsch[14a] reductive hydrogenation of carbon
In recent years our group has investigated the chemistry
of activated transition metal hydrides. It has been shown
that the carbyne ligand plays a prominent role in the elec-
tronic activation of hydride units.[1,2]
monoxide to hydrocarbons and oxygenates proposed by Ol-
The reactivity of 1 towards small unsaturated organic
molecules has been studied.[2] These studies, together with
density functional calculations,[3] have indicated an en-
hanced hydricity and a weakness of the WϪH bond, due
mainly to the mesityl carbyne ligand in the trans position,
which is known to exert a strong trans influence/effect.[4]
The use of dmpe ligands, which are strong σ-donors and
less effective π-acceptors than (for example) CO, should
lead to increased electron density on the metal, and also to
enhanced stability of the corresponding metal formyl moiet-
ies. Until 1973, when the first isolated anionic formyl com-
plex [(CO)4Fe(CHO)]Ϫ was reported by Collman and Win-
ter,[5] these compounds were conspicuous by their absence
from the chemical literature. The first neutral formyl com-
plex, Os(Cl)(CO)2(PPh3)2(CHO), was reported by Collins
and Roper in 1976.[6] In the same year, Casey, Gladysz, and
Winter[7] reported the first anionic formyl complexes,
formed by treatment of suitable hydride sources (in most
cases, main group metal ‘‘super hydrides’’) with metal car-
bonyls. Nelson,[8] however, demonstrated that a transition
metal hydride can also be effective as the hydride source.
The vast majority of known metal formyl complexes are,
however, thermally unstable with respect to decarbonyl-
ation.[9] Notable exceptions are the early transition metal
complexes,[10] the rhodium porphyrin hydride complex
RhOEP(H) (OEP ϭ octaethylporphyrin) described by Way-
land and co-workers,[11] and some actinohydrides[12] which
produce η2-formyl products. Transition metal formyl com-
[14b]
´
´
ive and Olive,
in which the insertion of carbon monox-
ide into a metalϪhydrogen bond to produce a formyl com-
plex is considered to be the initial step. Coordinated CO
can be inserted into the MϪH bond of metal hydrides,[15]
particularly when the reaction is driven by the oxophilic
character of early transition metals, allowing formation of
η2-formyl complexes. The generation of η1-formyl species is
generally thermodynamically unfavourable, as demon-
strated by several quantum chemical calculations.[16] We
therefore examined the reaction between 1 and CO bound
in metal carbonyl compounds, in order to explore the gen-
erality of WϪH addition across the CO bond.
Results and Discussion
Treatment of 1 with one equivalent of [Fe(CO)5] (at room
temperature in THF for a few minutes) did indeed quantit-
atively produce the dinuclear formyl-bridged complex trans-
W{(µ-OCH)Fe(CO)4}(CMes)(dmpe)2 (2, Scheme 1). The
mechanism is presumed to involve HϪ transfer to a CO
ligand, by direct nucleophilic attack on a metal-bound CO.
Dedieu and Nakamura have carried out extensive ab initio
SCF calculations on the hypothetical gas phase reaction be-
tween HϪ and [Fe(CO)5], and have concluded that for the
[(CO)4FeCHO]Ϫ ion, direct HϪ addition to an axial CO is
strongly exothermic and occurs without activation.[17] Ca-
sey and Neumann have reported a variety of metal formyl
compounds, including [Fe(CO)4CHO]Ϫ, resulting from the
reaction between [Naϩ][HB(OR)3Ϫ] and M(CO)x.[20]
[a]
Anorganisch-chemisches Institut, Universität Zürich,
Winterthurerstrasse 190, 8057 Zürich, Switzerland
Eur. J. Inorg. Chem. 2001, 1559Ϫ1565
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ1948/01/0606Ϫ1559 $ 17.50ϩ.50/0
1559

F. Furno, T. Fox, M. Alfonso, H. Berke
FULL PAPER
solid state it can be stored at room temperature under inert
atmosphere for several weeks without any deterioration.
The reaction between
1 and one equivalent of
[Re2(CO)10] in THF was followed by 1H and 31P{1H} NMR
spectroscopy and the primary insertion product (i.e.,
the formyl-bridged compound trans-W{(µ-OCH)Re2-
(CO)9}(CMes)(dmpe)2 (3a)) was detectable almost immedi-
ately (Scheme 3).
Scheme 1
Compound 2 was isolated, in 84% yield, as an orange,
microcrystalline powder after recrystallisation from a satur-
ated diethyl ether solution.
1
Among other resonances, the H NMR spectrum of 2
features a characteristic Hformyl nucleus signal at δ ϭ 13.67,
in the region reported for Kϩ[Fe(CO)4CHO]Ϫ (δ ϭ 15.0)[7d]
and mer-Mo{(µ-OCH)Fe(CO)4}(CO)(NO)(PMe3)3 (δ ϭ
14.09).[19a] The 31P{1H} NMR spectrum features a singlet
at δ ϭ 32.2 for the four equivalent phosphorus nuclei, with
satellites from coupling to 183W (1JPW ϭ 288 Hz). The
13C{1H} NMR spectrum includes a quintet at δ ϭ 298.6
for the Cformyl atom (3JCP ϭ 5 Hz), shifted by 39 ppm to
lower field as compared to [Fe(CO)4CHO]Ϫ,[7b] and an-
other quintet at δ ϭ 275.3 (2JCP ϭ 10 Hz) for the carbyne
carbon atom. These chemical shift values can be attributed
to more efficient electron withdrawal in the bridging coor-
dination mode. Evidence for the presence of a formyl ligand
is most easily found in the IR spectral data. The THF solu-
tion infrared spectrum of 2 shows three bands at 2045 (m),
1967 (m) and 1932 (s) cmϪ1 Ϫ attributable to the terminal
ν(CO) vibrations of the Fe(CO)4 unit Ϫ and one other band
at 1576 (m) for the iron formyl. This absorption pattern
closely resembles that of the reported anion
[Fe(CO)4CHO]Ϫ complex.[18] Compound 2 provided an ele-
mental analysis consistent with the proposed formula.
It was also expected that 2 would react further with ex-
cess 1. Reaction with up to 10 equivalents of 1 at room
temperature was therefore attempted, but no further trans-
formations could be observed, indicating that the remaining
carbonyls are inert towards further reduction to (for ex-
ample) a bis(formyl) complex (Scheme 2).
Scheme 3
This reaction proceeds smoothly at room temperature, re-
sulting in the formation of a clear orange/red solution.
Here, again, the bridging formyl group of 3a gives rise to
characteristic NMR resonances. The 1H NMR spectrum
shows the Hformyl resonance at δ ϭ 14.98, close to those
observed in Liϩ[Re2(CO)9(CHO)]Ϫ [15,26] and mer-Mo{(µ-
OCH)Re2(CO)9}(CO)(NO)(PMe3)3 (δ
ϭ
15.07).[19a]
31P{1H} NMR spectroscopy reveals a singlet at δ ϭ 29.9 for
the four equivalent phosphorus nuclei, with satellites from
coupling to 183W (1JPW ϭ 287 Hz). The 13C{1H} NMR
spectrum features a resonance at δ ϭ 295.1 for ReCHO.
During the course of the reaction, the THF solution
infrared spectrum had shown the ReCHO ν(CϭO) band at
1535 cmϪ1. However, unlike the reaction with [Fe(CO)5], an
equilibrium Ϫ lying to the right hand side, in favour of the
product (ratio of 1/3a, 2:3) Ϫ seems to have been reached
after two days. This was also observed in the case of the
similar
compound
mer-Mo{(µ-OCH)Re2(CO)9}(CO)-
(NO)(PMe3)3.[19a] At the same time, the emergence of a
series of large multiplets in the dmpe region of the 1H NMR
spectrum was observed. The 31P{1H} NMR spectrum also
displayed a number of new resonances. These signals are
attributable
to
the
isomeric
ionic
compound
[W(CMes)(CO)(dmpe)2]ϩ[Re2(CO)9H]Ϫ (3b). The colour of
the solution mixture was brown at this point, and after one
week at room temperature, almost 95% yield of this new
salt material 3b was observed spectroscopically (31P{1H}
Scheme 2
Steric hindrance probably makes the remaining CO li- NMR). The 31P{1H} NMR spectrum features four mul-
gands less susceptible to hydridic attack. On heating the tiplets of intensity 1:1:1:1 for the four chemically different
2
reaction mixture at 60 °C for two days, the expected hydride phosphorus atoms at δ ϭ 16.8 (ddd, JP3,P4 ϭ 5 Hz,
migration to the iron was not detected, and neither was CO 2JP3,P2 ϭ 21 Hz, JP3,P1 ϭ 63 Hz, JP3,W ϭ 249 Hz, P3),
2
1
ejection. Compound 2 seems to be unusually stable; in the 14.4 (dd, 2JP1,P3 ϭ 65 Hz, 2JP1,P4 ϭ 20 Hz, 1JP1,W ϭ 294 Hz,
1560
Eur. J. Inorg. Chem. 2001, 1559Ϫ1565

Reactivity of trans-W(CMes)(dmpe)2H with Group 7 and 8 Transition Metal Carbonyl Complexes
FULL PAPER
2
2
2
P1), 8.2 (ddd, JP4,P1 ϭ 20 Hz, JP4,P2 ϭ 25 Hz, JP4,P3
ϭ
5 Hz, 1JP4,W ϭ 202 Hz, P4) and Ϫ15.5 (dd, 2JP2,P3 ϭ 21 Hz,
2JP2,P4 ϭ 23 Hz, JP2,W ϭ 35 Hz, P2). The chemically dis-
1
tinct phosphorus atoms P1, P2, P3, and P4 have been as-
signed as described in Scheme 3. The assignments are in
agreement with previously published data[4] and reflect the
trans influence of the carbyne group on P2. It is therefore
weakly bonded to the tungsten centre with a small coupling
2
constant (1JP,W ϭ 35 Hz). For the same reason, JP2,P1 is
1
apparently so small as to be undetectable. The H NMR
spectrum shows a singlet at δ ϭ Ϫ17.47 for the ReϪH hy-
dride and a series of multiplets in the dmpe region, due to
the new arrangement of the dmpe ligands around the tung-
sten centre. The 13C{1H} NMR spectrum displays a mul-
tiplet at δ ϭ 293.7 for the mesitylidyne carbon, due to the
coupling with the four different phosphorus atoms, and an-
other multiplet at δ ϭ 230 for the WϪCO carbon atom
(2JC,P4 ϭ 11 Hz). The THF solution infrared spectrum dis-
plays, among other characteristic resonances, one band at
1915 cmϪ1 (s), consistent with a terminal WϪCO bond.
After isolation, 3b also gave satisfactory elemental microan-
alytical data.
An intrinsic chemical property of transition metal formyl
complexes is the capability to transfer a hydride ion to sev-
eral classes of substrate (such as ketones, alkyl halides, or
metal carbonyls), thereby acting as hydride donors. The lab-
ility of this metal formyl hydrogen was unambiguously
demonstrated with isolated formyl complexes about twenty
years ago.[7a,20,21] We propose, after initial attack by HϪ dir-
ectly on coordinated CO, an intramolecular hydride migra-
tion from the formyl to the Re, presumably with initial loss
of CO Ϫ i.e., a slow decarbonylation of 3a at room temper-
ature Ϫ to give the unsaturated complex 3aЈ, with sub-
sequent rearrangement around the tungsten centre to give
3b (Scheme 4). The assumed five-coordinate, square-pyram-
idal cationic intermediate 3aЈ is fluxional by the Berry
mechanism (pseudorotation) and gives rise to the trigonal-
bipyramidal 3bЈ intermediate, which is then trapped by the
free CO ligand to give 3b. It is interesting at this stage to
note that a CO ligand in a position trans to a carbyne unit
has never been observed.[22] The rate-determining step in
this reaction seems to be the decarbonylation step.
Scheme 4
duced. However, upon raising the temperature in the NMR
tube to Ϫ20 °C, the formyl signal gradually decreases, with
concomitant appearance of a new band (s, RuϪH) at δ
Ϫ12.05, assigned to 4. It is known that most of the formyl
intermediates are likely to decompose more rapidly than
they form.[23] These decomposition reactions of formyl
complexes, into the corresponding metal hydride with loss
of CO, have received a great deal of attention,[9,24] and rad-
ical processes have been invoked in many cases. It is still
not clear, however, whether this decomposition is deter-
mined by thermodynamic factors or is kinetic in origin.[25]
The balance between these will depend on the mechanism
of CO loss. For the anticipated cluster formyl complex
trans-W{(µ-OCH)Ru3(CO)11}(CMes)(dmpe)2, the decar-
bonylation step seems to be facilitated relative to that of 3a.
The fact that the stability of cluster formyl complexes is
lower than that of the related mononuclear species has al-
ready been noted by Thornback et al.[26] These workers sug-
gested that this instability is associated with the availability
of an ‘‘α-elimination’’ mechanism in cluster systems, related
to the β-elimination observed in mononuclear systems.
For mer-M(H)(CO)(NO)(PMe3)3 (M ϭ Mo, W), it has
been calculated that interaction with transition metal car-
bonyls such as [Fe(CO)5] and [Re2(CO)10] is determined by
secondary effects such as solvation or steric interactions,
since both carbonyl complexes possess comparable hydride
affinities.[19a][19b] For the related carbyne complexes, it is an-
ticipated that similar selectivities with a similar physical
background apply.
Scheme 5
Compound 1 reacts with one equivalent of the triruthen-
ium cluster [Ru3(CO)12] under ambient laboratory con-
The reaction proceeds smoothly at room temperature in
ditions
in
THF
to
afford
the
compound THF and is complete within a few minutes. Compound 4
[W(CMes)(CO)(dmpe)2]ϩ[Ru3(CO)11H]Ϫ (4) (Scheme 5), can be isolated in 82% yield as a brown, microcrystalline
presumably formed via a formyl intermediate. In fact, when powder after recrystallisation from a saturated diethyl ether
1
the reductive reaction is monitored at Ϫ50 °C in [D8]THF, solution. The H NMR spectrum features a characteristic
1
the H NMR spectrum displays a resonance at δ ϭ 15.6, singlet at δ ϭ Ϫ12.05 for the RuϪH hydride moiety in the
suggesting that a pendant formyl moiety has been pro- cluster anion [HRu3(CO)11]Ϫ,[27] which is consistent with
Eur. J. Inorg. Chem. 2001, 1559Ϫ1565
1561

F. Furno, T. Fox, M. Alfonso, H. Berke
FULL PAPER
the value reported in the literature (δ ϭ Ϫ12.9).[28] The elemental microanalysis. The 31P{1H} NMR spectrum of 4
31P{1H} NMR spectrum shows four different multiplet sig- (Figure 1) has been simulated and calculations carried out
2
nals of intensity 1:1:1:1 at δ ϭ 15.9 (ddd, JP3,P1 ϭ 66 Hz, in order to evaluate the coupling constants between the four
2JP3,P2 ϭ 20 Hz, 2JP3,P4 ϭ 6 Hz, 1JP3,W ϭ 269 Hz, P3), 13.9 different phosphorus nuclei (Table 1).
(dd, 2JP1,P3 ϭ 65 Hz, 2JP1,P4 ϭ 19 Hz, 1JP1,W ϭ 283 Hz, P1),
2
2
2
7.8 (ddd, JP4,P1 ϭ 19 Hz, JP4,P2 ϭ 25 Hz, JP4,P3 ϭ 6 Hz,
1JP4,W ϭ 223 Hz, P4), and Ϫ15.6 (dd, JP2,P3 ϭ 20 Hz,
2
Molecular Structure of 4
2JP2,P4 ϭ 25 Hz, JP2,W ϭ 20 Hz, P2) for the four non-
1
The structure of the separated ionic complex
[W(CMes)(CO)(dmpe)2]ϩ[Ru3(CO)11H]Ϫ (4) was finally es-
tablished unequivocally by single-crystal X-ray diffraction
(Figure 2 and Table 2). Suitable crystals were obtained by
slow cooling of a saturated diethyl ether solution to Ϫ30
°C. Unfortunately, the X-ray structure analysis of 4 was
hampered by the poor quality of the crystals, and attempts
to achieve suitable crystals of 2 and 3b were unsuccessful.
Therefore, large standard deviations were found for the
equivalent phosphorus nuclei. The different phosphorus
atoms P1, P2, P3, and P4 have been assigned as described
on Figure 1. Atom P2 is again, as in 3b, very weakly bound
1
with the tungsten centre, and therefore the JPW is very
1
small: JP2,W ϭ 20 Hz. This is not surprising, given the as-
sumed strong trans influence/effect of the carbyne ligand in
the trans position. Consequently, the value of the coupling
constant JP2,P1 is also very small and has been calculated
to be around 2 Hz (Table 1). This is also confirmed by the
X-ray structure (Figure 2), in which the long WϪP2 dis-
˚
bond lengths and angles. Selected bond lengths (A) and
angles (°) are listed in Table 3.
˚
tance [2.664(4) A], compared to the other WϪP bond
lengths, which are around 2.45, can be seen. Here, as for
3b, the 13C{1H} NMR spectrum once more shows a mul-
tiplet at δ ϭ 292, which corresponds to the Ccarbyne carbon;
this value is also further downfield than expected (shifted
by 31.6 ppm relative to 1), presumably due to the weakly
bound phosphorus atom in the trans position. The infrared
spectrum in THF solution exhibits, among other character-
istic bands, one band at 1900 cmϪ1 (s) for the W-CO ter-
minal carbonyl group. Compound 4 also gave a satisfactory
Figure 2. ORTEP plot of compound 4. Thermal ellipsoids are
drawn at the 30% probability level. Hydrogens (except H1) and the
Me carbon atoms from the dmpe ligands are omitted for clarity
Compound 4 adopts a pseudo-octahedral geometry, with
the carbyne and one phosphorus in axial positions and the
equator defined by 3 phosphorus atoms and the carbonyl
group.
Figure 1. Measured (upper) and simulated (lower) spectra for the
dmpe ligands in the 31P{1H} NMR spectrum of 4
Table 1. Calculated shifts and coupling constants between P1, P2,
P3, and P4 in compound 4
Conclusions
Nucleus Shift (ppm) Width (Hz) J, P1 (Hz) J, P3 (Hz) J, P4 (Hz)
P1
P2
P3
P4
13.9
Ϫ15.7
15.9
4.3
5.5
4.1
3.7
64.6
20.8
The results discussed above show that the tungsten hy-
dride complex trans-W(CMes)(dmpe)2H 1 readily reduces
group 7 and 8 transition metal carbonyls, acting as a hy-
dride-based nucleophile towards metal-bound CO.
2
23.5
7.7
19.5
5.8
1562
Eur. J. Inorg. Chem. 2001, 1559Ϫ1565

Reactivity of trans-W(CMes)(dmpe)2H with Group 7 and 8 Transition Metal Carbonyl Complexes
FULL PAPER
This observed high propensity towards carbonyl insertion
into the WϪH bond resembles that found for metallocene
hydride compounds with early transition metal centres.[29]
Table 2. X-ray crystal structure, data collection and refinement data
for 4
empirical formula
fw
C34H44O12P4Ru3W
1255.63
temperature [K]
wavelength [A]
cryst habit
cryst size
cryst syst
183(2)
0.71073
Experimental Section
˚
dark red block single crystal
0.18ϫ0.17ϫ0.14
triclinic
General: All manipulations of air-sensitive compounds were carried
out either in a Braun Labstar glovebox under nitrogen (dried if
appropriate) by conventional Schlenk techniques. Solvents were
dried with appropriate drying agents[30] and freshly distilled under
nitrogen prior to use. The different transition metal carbonyl com-
pounds Fe(CO)5 (Alfa products), Re2(CO)10 (Fluka), and
Ru3(CO)12 (Aldrich) were commercial products and used as re-
ceived. The deuterated solvents (C6D6, [D8]toluene, and [D8]THF)
were also obtained from commercial suppliers and distilled from
appropriate drying agents and vacuum transferred for storage in
Schlenk flasks fitted with Teflon stopcocks. The dmpe ligand was
¯
space group
P1
˚
a [A]
13.617(1)
13.6388(9)
14.8427(9)
101.211(8)
99.319(8)
117.923(7)
2285.1(3)
˚
b [A]
˚
c [A]
α [deg]
β [deg]
γ [deg]
3
˚
volume [A ]
Z
2
density (calcd) [Mg/mϪ3
]
1.825
3.673
1220
empirical
abs coeff [mmϪ1
F(000)
]
synthesized by following modified literature procedures.[31]
Ϫ
1H,
13C, and 31P NMR spectra were run either on a Varian Gemini 300
spectrometer operating at 300, 75.4, and 121.5 MHz, respectively,
or on a Bruker DRX 500 spectrometer at 500.2, 125.8, and
202.5 MHz, respectively. Values of δ(1 H), δ(13C), relative to SiMe4,
δ(31P) relative to 85% H3PO4. Ϫ Mass spectra (EI or FAB) were
recorded on a Finnigan MAT 8230 mass spectrometer. Ϫ IR spec-
tra: Bio-Rad FTS-45 instrument. Ϫ Elemental analyses: LECO
CHNS-932 machine. Ϫ The simulation of the 31P{1H} NMR spec-
trum was carried out with the aid of the gNMR 4.1 program. The
optimal fit was attained by simultaneous iteration of the chemical
shifts and coupling constants.
abs corr
Tmin/Tmax
θ range [deg]
index ranges
0.5577/0.6273
2.60 to 30.33
Ϫ19 Ͻ h Ͻ 19
Ϫ19 Ͻ k Ͻ 19
Ϫ20 Ͻ l Ͻ 20
27290
no. of reflns collected
no. of ind reflns
completeness to θ
refinement method
no. of data/restraints/params
extinction coefficient
12450 [R(int) ϭ 0.1016]
30.33°, 90.7%
Full-matrix, least-squares on F2
12450/0/483
0.0031 (5)
final R indices [I Ͼ 2σ(I)]
R indices (all data)
R1 ϭ 0.0827, wR2 ϭ 0.2169
R1 ϭ 0.1455, wR2 ϭ 0.2718
1.067
Preparation of trans-W(CMes)(dmpe)2(H) (1): The synthesis of 1
has already been published elsewhere.[2] Only the spectroscopic data
Goodness-of-fit on F2
1
for 1 are given here. Ϫ H NMR (C6D6, 298 K): δ ϭ 6.72 (s, 2 H,
Ϫ3
˚
largest diff peak and hole [e A
]
5.384 and Ϫ7.035
Mes), 2.62 (s, 6 H, 2CH3-Mes), 2.05 (s, 3 H, CH3-Mes), 1.67 (s br,
12 H, PMe), 1.52 (m br, 4 H, PCH2), 1.46 (s br, 12 H, PMeЈ), 1.42
2
1
(m br, 4 H, PCH2Ј), Ϫ6.58 (quint, JHP ϭ 32 Hz, JHW ϭ 31 Hz,
1 H, WH). 31P{1H} NMR (C6D6, 298 K): δ ϭ 24.4 (s, JPW
ϭ
1
281 Hz). 13C {1H} NMR (C6D6, 298 K): δ ϭ 260.4 (quint, JCP
ϭ
2
10 Hz, CMes), 151.5 (s, ipso-Mes), 137.4 (s, o-Mes), 135.4 (s, p-
Mes), 130.8 (s, m-Mes), 34.0 (quint, PCH2), 27.8 (m, PMe), 25.4
(m, PMeЈ), 22.6 (s, 2CH3-Mes), 21.5 (s, CH3-Mes). 183W{1H}
˚
Table 3. Selected bond lengths [A] and angles [°] for 4
[a]
selected angles [°][a]
˚
1
Selected bond lengths [A]
NMR ([D8]toluene, 298 K): δ Ϫ1612 (pseudo-q, JWP ϭ 281 Hz).
MS (FAB, toluene): m/z ϭ 615 [Mϩ], 310 (Mϩ Ϫ 2dmpe). Ϫ
WC22H44P4 (615.73): calcd. C 42.87, H 7.15%; found C 42.67, H
7.28%.
W(1)ϪC(1) 1.82(2)
C(1)ϪC(2) 1.48(2)
W(1)ϪC(1)ϪC(2) 169(1)
P(1)ϪW(1)ϪP(2) 77.0(1)
P(3)ϪW(1)ϪP(2) 98.8(1)
P(4)ϪW(1)ϪP(2) 94.0(1)
P(4)ϪW(1)ϪP(3) 77.7(1)
P(1)ϪW(1)ϪP(3) 172.2(1)
P(1)ϪW(1)ϪP(4) 95.8(1)
C(1)ϪW(1)ϪP(1) 87.7(5)
C(1)ϪW(1)ϪP(4) 102.7(5)
C(1)ϪW(1)ϪP(3) 98.0(5)
C(1)ϪW(1)ϪP(2) 158.4(4)
C(1)ϪW(1)ϪC(11) 87.4(6)
C(11)ϪW(1)ϪP(1) 93.7(5)
C(11)ϪW(1)ϪP(3) 92.0(5)
C(11)ϪW(1)ϪP(4) 166.4(4)
C(11)ϪW(1)ϪP(2) 78.6(4)
O(11)ϪC(11)ϪW(1) 175(1)
Ru(2)ϪRu(1)ϪRu(3) 59.64(5)
Ru(3)ϪRu(2)ϪRu(1) 60.26(5)
Ru(2)ϪRu(3)ϪRu(1) 60.10(5)
W(1)ϪP(1) 2.458(4)
W(1)ϪP(2) 2.664(4)
W(1)ϪP(3) 2.474(4)
W(1)ϪP(4) 2.566(4)
W(1)ϪC(11) 1.97(2)
C(11)ϪO(11) 1.17(2)
Ru(1)ϪRu(2) 2.829(2)
Ru(1)ϪRu(3) 2.833(2)
Ru(2)ϪRu(3) 2.816(1)
Preparation of trans-W{(µ-OCH)[Fe(CO)4]}(CMes)(dmpe)2 (2):
Compound 1 (30 mg, 0.0487 mmol) was dissolved in THF (5 mL)
and Fe(CO)5 (6.6 µL, 0.0487 mmol) added by microsyringe. The
mixture was stirred for a few minutes at room temperature. After
this period, the solvent was evaporated in vacuo and the precipitate
recrystallised from a diethyl ether solution at Ϫ30 °C to afford 2
as orange crystals. Yield: 33 mg (84%). Ϫ IR (cmϪ1, THF): 2045,
1967, 1932 [Fe(CO)4], 1576 (formyl), 894 (CMes). Ϫ 1H NMR
([D8]THF, 298 K): δ ϭ 13.67 (s, 1 H, OCH), 6.53 (s, 2 H, Mes),
2.25 (s, 6 H, 2CH3-Mes), 1.94 (s, 3 H, CH3-Mes), 1.40 (m br, 4 H,
PCH2), 1.34 (s br, 12 H, PMe), 1.28 (m br, 4 H, PCH2Ј), 1.20 (s br,
12 H, PMeЈ). Ϫ 31P{1H} NMR ([D8]THF, 298 K): δ ϭ 32.2 (s,
1JPW ϭ 288 Hz). Ϫ 13C{1H} NMR ([D8]THF, 298 K): δ ϭ 298.6
(q, 3JCP ϭ 5 Hz, OCH), 275.3 (quintet, 2JCP ϭ 10 Hz, CMes), 218.5
[s, Fe(CO)4], 151.2 (s, ipso-Mes), 135.2 (s, o-Mes), 133.1 (s, p-Mes),
1
128.3 (s, m-Mes), 33.5 (m, JCP ϭ 10 Hz, PCH2), 22.2 (s, 2CH3-
[a]
1
See Figure 2 for atom designations.
Mes), 22.1 (m, JCP ϭ 7 Hz, PMe), 20.4 (s, CH3-Mes), 17.4 (m,
Eur. J. Inorg. Chem. 2001, 1559Ϫ1565
1563

F. Furno, T. Fox, M. Alfonso, H. Berke
FULL PAPER
1
1JCP ϭ 7 Hz, PMeЈ). Ϫ C27H44P4O5FeW (811.58): calcd. C 39.92,
25 Hz, JP2,W ϭ 20 Hz, P2). Ϫ 13C{1H} NMR ([D8]THF, 298 K):
δ ϭ 292 (m, CMes), 229.1 (m, W-CO), 211 (s), 205 (s), 203 (s), 198
(s) Ru3(CO)11HϪ, 146.0 (s, ipso-Mes), 138.2 (s, o-Mes), 134.1 (s, p-
Mes), 130.5 (s, m-Mes), 12 multiplets between δ ϭ 36 and 15 for
the 12 different carbon atoms in the dmpe ligands, 22.6 (s, 2CH3-
Mes), 20.1 (s, CH3-Mes). Ϫ C34H44P4O12Ru3W (1254.34): calcd. C
32.51, H 3.51%; found C 32.31, H 3.70%.
H 5.42%; found C 40.21, H 4.90%.
Preparations of trans-W{(µ-OCH)[Re2(CO)9]}(CMes)(dmpe)2 (3a)
and [W(CMes)(CO)(dmpe)2]؉[Re2(CO)9H]؊ (3b): Compound 1
(30 mg, 0.0487 mmol) was dissolved in THF (5 mL), Re2(CO)10
(32 mg, 0.0487 mmol) was added, and the mixture was stirred for
a few minutes at room temperature. After this period, NMR exam-
ination in [D8]THF already showed a spectroscopically small
amount (36%) of 3a. After two days at room temperature, the
amount of 3a was about 67%. Ϫ IR (cmϪ1, THF): 1535 (ReCHO).
Crystallography: Single crystals of 4, of rather poor quality for X-
ray studies, were obtained directly from the preparation as de-
scribed in the Experimental Section. A dark red crystal of 4 with
dimensions 0.18 ϫ 0.17 ϫ 0.14 mm was selected and mounted on
the top of a glass fibre covered with a small amount of hydrocarbon
oil and immediately placed on the goniometer of a Stoe IPDS dif-
fractometer. The radiation used was Mo-Kα (0.71073), monochro-
matised by a crystal of graphite [the crystal-to-image plate distance
was set to 50 mm (θmax ϭ 30.33°)]. Because of the long exposure
time, the -oscillation scan mode was selected and a total of 223
images were collected at 183 K. Each exposure required 10 min.
and covered 0.9° in . The intensities were integrated after using a
dynamic peak profile analysis, and estimated mosaic spread check
was performed to prevent overlapping intensities. 7998 reflections
were selected out of the whole limiting sphere for the cell parameter
refinement. A total of 27290 reflections were collected, of which
12450 reflections were unique (Rint ϭ 0.1016). A numerical ab-
sorption correction based on measured crystal faces was applied
without any improvement. Therefore, an empirical absorption cor-
rection utilising the program (ABSCOR)[32] was considered (max-
imum and minimum values of the transmission factor were 0.6273
and 0.5577).
1
Ϫ H NMR ([D8]THF, 298 K): δ ϭ 14.98 (s, 1 H, OCH), 6.50 (s,
2 H, Mes), 2.31 (s, 6 H, 2CH3-Mes), 1.91 (s, 3 H, CH3-Mes), large
multiplets for the dmpe ligands between δ ϭ 1.40 and 1.20. Ϫ
31P{1H} NMR ([D8]THF, 298 K): δ ϭ 29.9 (s, JPW ϭ 287 Hz). Ϫ
1
13C{1H} NMR ([D8]THF, 298 K): selected data: δ ϭ 295.1 (Re-
CHO), 205.1, 202.5, 195.4, 191.5 (Re-CO).
After one week at room temperature, an almost quantitative yield
of 3b was observed spectroscopically, and recrystallisation from a
saturated diethyl ether solution gave a final yield of 72%.
Compound 4 crystallised in the triclinic crystal system. The space
group P1 was assumed and confirmed by the successful solution
IR (cmϪ1, THF): 2086, 2028, 1974, 1925, 1895 (Re2(CO)9HϪ), 1915
(WϪCO), 891 (CMes). Ϫ 1H NMR ([D8]THF, 298 K): δ ϭ 6.71 (s,
2 H, Mes), 2.51 (s, 6 H, 2CH3-Mes), 2.01 (s, 3 H, CH3-Mes), series
of large multiplets for the dmpe ligands between δ ϭ 1.87 and 1.34,
Ϫ17.47 (s, Re-H). Ϫ 31P{1H} NMR ([D8]THF, 298 K): δ ϭ 16.8
¯
and refinement of the structure. The structure was solved by a com-
bination of direct methods and difference Fourier synthesis
(SHELXS-97)[33] and refined on F2 by full-matrix, least-squares
techniques (SHELXL-97).[33] All non-hydrogen atoms were refined
with anisotropic thermal parameters, except C30 which resulted as
non-positive definite. All hydrogen atom positions on the ligands
were calculated assuming idealised geometries. The position of the
hydride was found in a difference Fourier synthesis, but its position
could not be refined. It was added as a constant contribution with-
out refinement. At convergence, R1 ϭ 0.0827, wR2 ϭ 0.2169 and
GooF ϭ 1.067 for 483 variables refined using 12450 unique data.
2
2
2
1
(ddd, JP3,P4 ϭ 5 Hz, JP3,P2 ϭ 21 Hz, JP3,P1 ϭ 63 Hz, JP3,W
249 Hz, P3), 14.4 (dd, JP1,P3 ϭ 65 Hz, JP1,P4 ϭ 20 Hz, JP1,W
ϭ
ϭ
ϭ
ϭ
2
2
1
2
2
2
294 Hz, P1), 8.2 (ddd, JP4,P1 ϭ 20 Hz, JP4,P2 ϭ 25 Hz, JP4,P3
1
2
2
5 Hz, JP4,W ϭ 202 Hz, P4), Ϫ15.5 (dd, JP2,P3 ϭ 21 Hz, JP2,P4
23 Hz, JP2,W ϭ 35 Hz, P2). Ϫ 13C{1H} NMR ([D8]THF, 298 K):
1
2
δ ϭ 293.7 (m, CMes), 230.0 (m, JC,P4 ϭ 11 Hz, W-CO), 202.2,
201.9, 199.8, 198.7, 190.5 (5s, Re2(CO)9HϪ), 147.0 (s, ipso-Mes),
139.2 (s, o-Mes), 138.3 (s, p-Mes), 129.3 (s, m-Mes), 12 multiplets
between δ ϭ 32 and 14 for the 12 different carbon atoms in the
Supplementary Material: Crystallographic data for the structural
analysis has been deposited with the Cambridge Crystallographic
Data Centre, CCDC No 150504 for compound 4. Copies of this
information may be obtained free of charge from the Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [Fax: (in-
dmpe ligands, 21.6 (s, 2CH3-Mes), 20.9 (s, CH3-Mes).
Ϫ
C32H44P4O10Re2W·1/2Et2O (1305.13): calcd. C 30.34, H 3.75%;
found C 30.82, H 3.40%.
Preparation of [W(CMes)(CO)(dmpe)2]؉ [Ru3(CO)11H]؊ (4): A ternat.) ϩ44Ϫ1223/336-033; E-mail: deposit@ccdc.cam.ac.uk, or
mixture of 1 (30 mg, 0.0487 mmol) and Ru3(CO)12 (31.10 mg,
0.0487 mmol) in THF (5 mL) was stirred for 1 hour at room tem-
perature. After this period, the solvent was evaporated in vacuo
and the precipitate recrystallised at Ϫ30 °C from a diethyl ether
solution to afford 4 as brown microcrystals. Yield: 24.6 mg (82%).
Ϫ IR (cmϪ1, THF): 2073, 2014, 1987, 1952 (Ru3(CO)11HϪ), 1900
(WϪCO), 892 (CMes). Ϫ 1H NMR ([D8]THF, 298 K): δ ϭ 6.49 (s,
2 H, Mes), 2.27 (s, 6 H, 2CH3-Mes), 1.90 (s, 3 H, CH3-Mes), series
of large multiplets for the dmpe ligands between δ ϭ 1.47 and 1.08,
Ϫ12.05 (s, Ru-H). Ϫ 31P{1H} NMR ([D8]THF, 298 K): δ ϭ 15.9
http://www.ccdc.cam.ac.uk].
Acknowledgments
Financial support for this work from the Swiss National Science
Foundation and from the University of Zürich is gratefully
acknowledged.
[1]
E. Bannwart, H. Jacobsen, F. Furno, H. Berke, Organometallics
2000, 19, 3605.
2
2
2
1
(ddd, JP3,P1 ϭ 66 Hz, JP3,P2 ϭ 20 Hz, JP3,P4 ϭ 6 Hz, JP3,W
ϭ
ϭ
ϭ
ϭ
[2]
[2a] F. Furno, T. Fox, H. W. Schmalle, H. Berke, Organometallics
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H. Jacobsen, F. Furno, H. Berke, manuscript in preparation.
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283 Hz, P1), 7.8 (ddd, JP4,P1 ϭ 19 Hz, JP4,P2 ϭ 25 Hz, JP4,P3
1
2
2
[3]
6 Hz, JP4,W ϭ 223 Hz, P4), Ϫ15.6 (dd, JP2,P3 ϭ 20 Hz, JP2,P4
1564
Eur. J. Inorg. Chem. 2001, 1559Ϫ1565

Reactivity of trans-W(CMes)(dmpe)2H with Group 7 and 8 Transition Metal Carbonyl Complexes
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1565