Multisite reactivity of the central Mo2CP core in the unsaturated carbyne-bridged complex [Mo2(η5-C 5H5)2(μ-CPh)(μ-PCy2)(CO) 2]

Article abstract of DOI:10.1021/om2003738

The title compound reacted with HBF₄OEt₂ at room temperature to give a mixture of the agostic-like, phosphine-bridged complex [Mo₂Cp₂(μ-CPh)(μ-κ¹: η²-PHCy₂)(CO)₂]BF

Full text of DOI:10.1021/om2003738

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pubs.acs.org/Organometallics
Multisite Reactivity of the Central Mo2CP Core in the Unsaturated
Carbyne-Bridged Complex [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(CO)2]
M. Angeles Alvarez, M. Esther García, Sonia Menꢀendez, and Miguel A. Ruiz*
Departamento de Química Orgꢀanica e Inorgꢀanica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain
S Supporting Information
b
ABSTRACT: The title compound reacted with HBF4 OEt2 at room temperature to give a
3
mixture of the agostic-like, phosphine-bridged complex [Mo2Cp2(μ-CPh)(μ-k1:η2-PHCy2)-
(CO)2]BF4 (major) and the carbene-bridged complex [Mo2Cp2(μ-η1:η2-CHPh)(μ-PCy2)-
(CO)2]BF4 (minor). It readily added a molecule of HCtCCO2Me or a single Se atom at its
Mo2C(carbyne) center to give with high yield the corresponding propenylylidene- or
selenoacyl-bridged derivatives [Mo2Cp2{μ-η2:η3-CPhCHC(CO2Me)}(μ-PCy2)(CO)2]
and [Mo2Cp2{μ-η,k:η,k-C(Ph)Se}(μ-PCy2)(CO)2], respectively. In contrast, the addition
of a neat donor at the metal site can induce a reversible carbyneꢀcarbonyl coupling, as
observed in the reaction with N2CPh2 to give the ketenyl derivative [Mo2Cp2{μ-η1:η2-
C(Ph)CO}(μ-PCy2)(CO)(k1-N2CPh2)].
Chart 1
he chemistry of carbyne complexes is an intensively studied
area within organometallic science. These compounds usual-
T
ly display a high reactivity derived from the multiple nature of
their metalꢀcarbon bonds in either the terminal or the edge-
bridging coordination modes (A and B in Chart 1),1 and they are
also involved in several industrial processes of interest such as the
FischerꢀTropsch (FT) synthesis of hydrocarbons from syngas
(CO + H2)2 and alkyne metathesis.3 The reactivity of the edge-
bridged complexes can be further increased by the presence of
multiple metalꢀmetal bonds. Moreover, the chemistry of a
carbyne ligand at such unsaturated dimetal centers can be
considered as a crude but simple model of the chemical behavior
of related surface species formed in different heterogeneously
catalyzed reactions, notably the CꢀC coupling processes involved
inthe FTsynthesis. Indeed, ourpreviousstudiesonthe behavior of
the unsaturated methoxycarbyne-bridged complexes [Mo2Cp2-
(μ-COMe)(μ-PCy2)(μ-CO)]4 and [Mo2Cp2(μ-COMe)(μ-PCy2)-
(CO)2]5 revealed a high and multipositional reactivity of these
electron-deficient dimetal centers under mild conditions, includ-
ing some interesting CꢀC bond formation processes.4d,5c
Recently we described efficient synthetic procedures for the
preparation of the unsaturated benzylidyne complexes [Mo2Cp2-
(μ-CPh)(μ-PCy2)(μ-CO)] and [Mo2Cp2(μ-CPh)(μ-PCy2)-
(CO)2],6 which are structurally and electronically related to the
mentioned methoxycarbyne complexes, this providing an ideal
opportunity to compare the multisite reactivity of all these
unsaturated carbyne complexes. Initial studies on the chemical
behavior of the 30-electron monocarbonyl complex revealed
the involvement of the carbyne ligand in unusual CꢀC and CꢀP
coupling processes, but only at cationic derivatives following
alkylation or oxidation steps.7 In its neutral state, this molecule
seems to be rather unreactive toward small unsaturated organic
molecules such as alkynes or diazoalkanes. We then turned our
attention to the 32-electron complex [Mo2Cp2(μ-CPh)-
(μ-PCy2)(CO)2] (1), which has a dimetal core bridged by only
two ligands and therefore is more accessible to external reagents
(Chart 1). In this paper we report our preliminary studies on the
reactions of 1 with different reagents ranging from protonic acids
or small unsaturated organic molecules such as alkynes and
diazoalkanes to simple elements such as chalcogens (Scheme 1).
From this we conclude that compound 1 is more reactive than
the triply bridged [Mo2Cp2(μ-CPh)(μ-PCy2)(μ-CO)] as antici-
pated, but also that this dicarbonyl complex displays a multisite
reactivity that is somewhat unexpected since all elements of the
central Mo2CP core can be involved in these reactions, that is,
not only the MoꢀMo and MoꢀC bonds, but also the MoꢀP
bonds of the dicyclohexylphosphide bridge.
Compound 1 is basic enough to be protonated by strong acids
such as HBF4 OEt2. However, this reaction unexpectedly gives a
3
Received: May 5, 2011
Published: June 23, 2011
r
2011 American Chemical Society
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dx.doi.org/10.1021/om2003738 Organometallics 2011, 30, 3694–3697
|

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Scheme 1
Figure 1. ORTEP drawing (30% probability) of compound 4, with
H atoms (except H10) and cyclohexyl rings (except the C1 atoms) omitted
for clarity. Selected bond lengths (Å) and angles (deg): Mo1ꢀMo2 =
2.8349(5), Mo1ꢀP1 = 2.475(1), Mo1ꢀC1 = 1.971(5), Mo1ꢀC3 =
2.399(4), Mo1ꢀC10 = 2.279(5), Mo1ꢀC11 = 2.198(5), Mo2ꢀ
P1 = 2.416(1), Mo2ꢀC2 = 1.991(5), Mo2ꢀC3 = 2.184(4), Mo2ꢀ
C11 = 2.193(5), C3ꢀC10 = 1.402(6), C10ꢀC11 = 1.446(6),
C11ꢀC12 = 1.458(7), C12ꢀO3 = 1.210(6), C12ꢀO4 = 1.350(6); Mo2ꢀ
Mo1ꢀC1 = 117.9(1), Mo1ꢀMo2ꢀC2 = 84.0(1).
mixture of two quite air-sensitive products when carried out in
dichloromethane solution at room temperature (Scheme 1): the
agostic-like, phosphine-bridged complex [Mo2Cp2(μ-CPh)-
(μ-k1:η2-PHCy2)(CO)2]BF4 (2)8 and the carbene-bridged
complex [Mo2Cp2(μ-η1:η2-CHPh)(μ-PCy2)(CO)2]BF4 (3).9
Although we have not been able to separate these products by
fractional crystallization so far, the phosphine complex 2 could be
obtained as an essentially pure material by carrying out the
protonation reaction at 243 K, thus facilitating the spectroscopic
characterization of these products. Moreover we note that com-
pound 2 does not transform into 3 at room temperature or even
upon warming it at ca. 323 K in dichloromethane solution.
The formation of 2 follows from the protonation of the neutral
substrate 1 at a MoꢀP bond of the bridging PCy2 ligand, an
unusual and orbital-controlled reaction recently described by us
for isoelectronic complexes of the type [Mo2Cp2(μ-PR2)-
(μ-PR02)(CO)2] having electron-rich PR2 bridges, to give
the corresponding cations [Mo2Cp2(μ-PR02)(μ-k1:η2-PHR2)-
(CO)2]+.5b,10 Indeed, a DFT calculation on the related carbyne
complex [Mo2Cp2{μ-C(CO2Me)}(μ-PCy2)(CO)2] indicates
that the HOMOꢀ4 orbital in this molecule has a large MoꢀP
σ-bonding character,5a thus pointing to the formation of 2 as an
orbital-controlled event. In contrast, the mentioned calculation
reveals a significant negative charge at the carbyne C atom, thus
suggesting that the formation of the carbene complex 3 would be
favored on electrostatic grounds. The presence of the agostic-like
MoꢀHꢀP interaction in 2 is denoted by the appearance of
resonance of the phenyl ring is considerably shielded (δC 115.2 ppm),
this being taken as a piece of evidence for the coordination of
at least that carbon atom to one of the molybdenum atoms
(μ-η1:η2-mode, Scheme 1). We note that a few arylcarbene
complexes exhibiting closely related interactions of the ipso and
ortho carbons of their aryl rings (μ-η1:η3-mode) have been
structurally characterized previously.11 The protonation reac-
tions of the unsaturated complex 1 just discussed share some
analogies, but also significant differences, with the analogous
reactions of the electron-precise alkylidyne complexes [Mo2Cp2-
(μ-CH2R)(μ-SMe)3] (R = 4-Me-C6H4, n-Pr).12 In fact, the latter
reactions give alkylidene derivatives displaying agostic CꢀH
3 3 3
Mo (instead of CꢀC Mo) interactions when carried out in
3 3 3
dichloromethane solutions, but they result in the loss of an
HSMe molecule when carried out in acetonitrile solution.12c
The unsaturated nature and relatively unprotected central
Mo2PC core of 1 facilitates the addition of small unsaturated
molecules such as alkynes and diazoalkanes, as well as some
concomitant CꢀC coupling processes. For instance, compound 1
reacts with methyl propiolate at 333 K to give with high
yield the corresponding propenylylidene derivative [Mo2Cp2-
{μ-η2:η3-CPhCHC(CO2Me)}(μ-PCy2)(CO)2] (4) resulting
from the specific coupling of the carbyne ligand to the terminal
carbon of the alkyne.13 This behavior parallels that previously
observed for the isoelectronic methoxycarbyne complex [Mo2Cp2-
(μ-COMe)(μ-PCy2)(CO)2]5c and the heterometallic complex
[FeMoCp{μ-C(p-tol)}(CO)5].14 In the crystal (Figure 1),15
the intrinsic asymmetry of the bridging hydrocarbyl ligand
(providing the Mo1 atom with one more electron) is balanced
by a tighter binding of the P and C3 atoms to Mo2.
1
relatively shielded 31P and H NMR resonances (131.4 and
ꢀ4.30 ppm, respectively) with strongly reduced one-bond
mutual coupling (117 Hz), that is, about half the usual values
for comparable “normal” PꢀH bonds.10 For complex 3, the
appearance in the 13C NMR spectrum of a relatively shielded CH
resonance at 180 ppm denotes the transformation of the former
carbyne ligand into a bridging carbene group. Although the
formation of the latter ligand in principle would reduce the
electron count of the dimetal center and thus would increase its
electronic unsaturation, there is no evidence of an agostic CꢀH
interaction of the carbene ligand with the dimetal center to
mitigate such an unsaturation. Instead, we note that the ipso
In contrast, the addition of a molecule of N2CPh2 to the
unsaturated compound 1 induces a CꢀC coupling process of the
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Figure 2. ORTEP drawing (30% probability) of compound 5, with
H atoms and cyclohexyl and phenyl rings (except the C1 atoms) omitted
for clarity. Selected bond lengths (Å) and angles (deg): Mo1ꢀMo2 =
2.8935(9), Mo1ꢀP1 = 2.364(2), Mo1ꢀC1 = 1.932(8), Mo1ꢀC2 =
2.163(7), Mo1ꢀC3 = 2.203(7), Mo2ꢀP1 = 2.432(2), Mo2ꢀC3 =
2.148(7), Mo2ꢀN1=1.748(5), N1ꢀN2=1.338(7), N2ꢀC10 = 1.306(8),
C3ꢀC2 = 1.398(9), C2ꢀO2 = 1.215(8); Mo2ꢀMo1ꢀC1 = 96.4(2),
Mo1ꢀMo2ꢀN1 = 103.6(2). Mo2ꢀN1ꢀN2 = 174.6(5), N1ꢀN2ꢀ
C10 = 120.0(6), C3ꢀC2ꢀO2 = 142.3(7), Mo1ꢀC2ꢀO2 = 144.2(5).
Figure 3. ORTEP drawing (30% probability) of compound 7, with
H atoms and cyclohexyl and phenyl rings (except the C1 atoms) omitted
for clarity. Selected bond lengths (Å) and angles (deg): Mo1ꢀMo2 =
2.8950(3), Mo1ꢀP1 = 2.4415(6), Mo1ꢀC1 = 1.921(2), Mo1ꢀC3 =
2.180(2), Mo1ꢀSe1 = 2.5611(3), Mo2ꢀP1 = 2.4084(6), Mo2ꢀC2
= 1.977(2), Mo2ꢀC3 = 2.121(2), Mo2ꢀSe1 = 2.5916(3); Se1ꢀC3 =
1.924(2), Mo2ꢀMo1ꢀC1 = 113.0(1), Mo1ꢀMo2ꢀC2 = 79.5(1).
The unsaturated nature of 1 also facilitates the addition under
mild conditions of single chalcogen atoms to the central Mo2C
triangle to give symmetrically bridging (μ-η,k:η,k mode) chal-
coacyl ligands, thus paralleling the behavior of related hetero-
metallic complexes of the type [MFeL(μ-CR)(CO)x] toward
elemental S and Se (M = Mo, W; L = Cp or related ligand; R =
p-tol, Xyl; x = 5, 6).22 For instance, compound 1 reacts with gray
selenium at 333 K to give the selenoacyl derivative [Mo2Cp2{μ-
η,k:η,k-C(Ph)Se}(μ-PCy2)(CO)2] (7) almost quantitatively.23
In the crystal (Figure 3),24 the selenioacyl ligand displays single-
bond lengths of ca. 2.58 Å (SeꢀMo) and 2.15 Å (C3ꢀMo) to
both metal atoms. These values are comparable to those recently
measured for the heterometallic complex [MoRh{μ-η,k:η,k-
C(R)Se}Cl(CO)2(PPh3){HB(pzMe2)3}] (R = C2SiMe3), which
appears to be the only other selenoacyl-bridged complex
structurally characterized so far.25 As a result of this coordina-
tion mode, the selenoacyl ligand in 7 acts as a five-electron
donor to the dimetal center, which then becomes electron-
precise, in agreement with the measured intermetallic distance
of ca. 2.90 Å.
carbyne with a carbonyl ligand, rather than a coupling with the
added reagent. Actually, this reaction takes place only at very high
concentrations and gives a mixture of two diazoalkane com-
plexes: the ketenyl complex [Mo2Cp2{μ-η1:η2-C(Ph)CO}-
(μ-PCy2)(CO)(k1-N2CPh2)] (5)16 and its carbyne derivative
[Mo2Cp2(μ-CPh)(μ-PCy2)(CO)(k1-N2CPh2)] (6).17 Indepen-
dent experiments revealed that these species are related by
carbonylation/decarbonylation processes, therefore allowing
their selective preparation. Thus, the above mixture can be
transformed into pure 5 by reacting it with CO (ca. 3 atm) in
dichloromethane solution at room temperature. In contrast,
heating at 353 K a toluene solution of this mixture for 30 min
yields pure compound 6 (see the Supporting Information). The
formation of 5 gives experimental support to our previous
hypothesis that the formation of the ketenyl complex [Mo2Cp2-
{μ-η1:η1-C(Ph)CO}(μ-PCy2)(CO)2] upon carbonylation of 1
would imply the coordination of CO to the unsaturated dimetal
center of 1 followed by reorganization, rather than arising from
direct attack of CO to the electron-rich carbyne ligand.6
The geometrical parameters of the terminal diazoalkane ligand
in 5 (Figure 2)18 indicate that this group acts as a four-electron
donor (imido-like coordination) to the dimetal center,19 and this
is balanced by an asymmetric coordination (μ-η1:η2 mode) of
the ketenyl ligand, in turn acting as a three-electron donor. As a
result, the molecule formally is electron-precise, as found pre-
viously for the related diphenylphosphide complex [W2Cp2-
(μ-PPh2)2(CO)(k1-N2CPh2)],20 and this is in agreement with
the relatively large intermetallic length of ca. 2.90 Å. The same
comment applies to compound 6, except that the ketenyl ligand
is here being replaced by a bridging carbyne, as denoted by the
presence in its 13C NMR spectrum of a strongly deshielded
resonance at 373.5 ppm. We finally note that the asymmetric
coordination mode of the ketenyl ligand found in 5 has been
previously characterized in a few, usually heterometallic sub-
strates,21 the only homometallic precedent being the ditungsten
complex [W2(μ-Br)Br2{μ-η1:η2-C(4-Me-C6H4)CO}(CO){μ-
F2PN(Me)PF2}2].21a
In summary, we have shown that the unsaturated benzyliyne
complex 1 displays a multisite reactivity of its central Mo2PC
core involving not only the addition of neat electron donors at
the electron-deficient metal site (reaction with N2CPh2) or the
addition of ambiphilic reagents to the Mo2C face (reactions with
selenium and HCtCCO2Me) but also the addition of neat
acceptors either at the carbyne atom or at the MoꢀP bonds
(protonation reaction). Further studies are now in progress to
fully explore the synthetic potential of this 32-electron carbyne-
bridged dimolybdenum complex.
’ ASSOCIATED CONTENT
S
Supporting Information. Text giving experimental pro-
b
cedures and spectroscopic and microanalytical data for new
compounds (PDF) and a CIF file giving crystallographic data
for compounds 4, 5, and 7. This material is available free of charge
via the Internet at http://pubs.acs.org.
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’ AUTHOR INFORMATION
24, 6268. (c) Le Goff, A.; Le Roy, C.; Pꢀetillon, F. Y.; Schollhammer, P.;
Talarmin, J. Organometallics 2007, 26, 3607.
(13) Selected data for 4: ν(CO) (CH2Cl2): 1916 (m), 1886 (vs) cmꢀ1
.
Corresponding Author
*E-mail: mara@uniovi.es.
31P{1H} NMR (121.48 MHz, CD2Cl2): δ 140.3. 13C{1H} NMR (75.46
MHz, CD2Cl2):δ 137.7 (s, μ-CPh), 92.1 (d, JCP = 5, MoCH), 78.4 (d, JCP
28, μ-CCO2Me).
=
(14) (a) García, M. E.; Jeffery, J. C.; Sherwood, P.; Stone, F. G. A.
J. Chem. Soc., Dalton Trans. 1988, 2443. (b) García, M. E.; Tran-Huy,
N. H.; Jeffery, J. C.; Sherwood, P.; Stone, F. G. A. J. Chem. Soc., Dalton
Trans. 1987, 2201.
’ ACKNOWLEDGMENT
We thank the DGI of Spain (Project CTQ2009-09444) and
the Consejería de Educaciꢀon de Asturias (grant to S.M.) for
supporting this work.
(15) X-ray data for 4: orange crystals, triclinic (P1), a = 9.8540(5) Å,
b = 11.4584(6) Å, c = 16.1062(8) Å, R = 76.032(3)°, β = 79.622(4)°,
γ = 81.141(3)o, V = 1724.3(2) Å3, T = 100 K, Z = 2, R = 0.0551
(observed data with I > 2σ(I)), GOF = 1.031.
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CD2Cl2): δ 234.4 (d, JCP = 12, MoCO), 226.0 [s, MoC(O)], 136.5 (s,
N2CPh2), 134.4 (s, μ-CPh).
(17) Selected data for 6: ν(CO) (CH2Cl2): 1872 (s) cm .
ꢀ1 31P{1H}
NMR (161.97 MHz, CD2Cl2): δ 188.7. 13C{1H} NMR (100.61 MHz,
CD2Cl2): δ 373.5 (d, JCP = 6, μ-CPh), 248.5 (d, JCP = 10, MoCO), 133.9
(s, N2CPh2).
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(23) Selected data for 7: ν(CO) (THF): 1889 (sh), 1872 (vs) cmꢀ1
.
31P{1H} NMR (121.48 MHz, CD2Cl2): δ 124.3. 13C{1H} NMR
(100.61 MHz, CD2Cl2, 253 K): δ 89.6 (s, μ-CSe).
(24) X-ray data for 7: brown crystals, monoclinic (P21/c), a =
10.0964(4) Å, b = 15.8350(6) Å, c = 21.7892(8) Å, β = 115.617(2)o,
V = 3141.2(2) Å3, T = 100 K, Z = 4, R = 0.0428 (observed data with I >
2σ(I)), GOF = 1.039.
(8) Selected data for 2: ν(CO) (CH2Cl2): 1981 (w), 1958 (vs) cmꢀ1
.
1H NMR (400.13 MHz, CD2Cl2): δ ꢀ4.30 (d, JPH = 117, μ-PH).
31P{1H} NMR (161.97 MHz, CD2Cl2): δ 131.4. 13C{1H} NMR (100.61
MHz, CD2Cl2, 253 K): δ 415.3 (s, μ-CPh).
(9) Selected data for 3: ν(CO) (CH2Cl2): 1981 (w), 1958 (vs) cmꢀ1
.
(25) Caldwell, L. M.; Cordiner, R. L.; Hill, A. F.; Wagler, J. Organo-
metallics 2010, 29, 1526.
1H NMR (400.13 MHz, CD2Cl2, 213 K): δ 9.18 (s, 1H, μ-CH). 31P{1H}
NMR (161.97 MHz, CD2Cl2, 213 K): δ 214.8. 13C{1H} NMR (100.61
MHz, CD2Cl2, 213 K): δ 180.0 (s, μ-CHPh), 115.2 [s, C1(Ph)].
(10) Alvarez, M. A.; García, M. E.; Martínez, M. E.; Ramos, A.; Ruiz,
M. A.; Sꢀaez, D. Inorg. Chem. 2006, 45, 6965.
(11) (a) Jeffery, J. C.; Moore, I.; Razay, H.; Stone, F. G. A. J. Chem.
Soc., Chem. Commun. 1981, 1255. (b) Fischer, H.; Schmid, J.; Riede, J.
J. Organomet. Chem. 1988, 355, 219. (c) Tang, Y.; Sun, J.; Chen, J.
J. Chem. Soc., Dalton Trans. 1998, 931.
(12) (a) Cabon, N.; Schollhammer, P.; Pꢀetillon, F. Y.; Talarmin, J.
Organometallics 2002, 21, 448. (b) Cabon, N.; Le Goff, A.; Le Roy, C.;
Pꢀetillon, F. Y.; Schollhammer, P.; Talarmin, J. Organometallics 2005,
3697
dx.doi.org/10.1021/om2003738 |Organometallics 2011, 30, 3694–3697