Alkyne to carbyne coupling reactions of the unsaturated methoxycarbyne-bridged complex [Mo2(η5-C5H5)2(μ-COMe)(μ-PCy2)(CO)2]

Garcı́a, M. Esther; García‐Vivó, Daniel; Ruiz, Miguel A.

doi:10.1016/j.jorganchem.2010.03.020

Cited by 6 publications

(5 citation statements)

References 40 publications

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“…Related complex [Mo 2 Cp 2 {μ-κ 2 :η 3 -CPhC(CO 2 Me)C(CO 2 Me)}(μ-PCy 2 )(CO) 2 ] ( 7b ) could be obtained when using the internal alkyne dimethyl acetylenedicarboxylate, although in that case the reaction had to be carried out at 393 K to overcome the higher steric barrier involved in the corresponding C–C coupling. In any case, we note that this behavior is comparable to the one previously found for related carbyne-bridged complexes such as dimolybdenum complex [Mo 2 Cp 2 (μ-COMe)(μ-PCy 2 )(CO) 2 ] or heterometallic [FeMoCp{μ-C( p -tol)}(CO) 5 ] …”

Section: Resultssupporting

confidence: 88%

“…The structure of compound 7a was determined by an X-ray study during our preliminary exploration on the chemistry of 1 (Figure ) and turned out to be very similar to that of trans -[Mo 2 Cp 2 {μ-κ 2 :η 3 -C(OMe)CHC( p -tol)}(μ-PCy 2 )(CO) 2 ], a molecule which we have discussed in detail previously; therefore, no further discussion on the structural aspects of compounds 7 is needed.…”

Section: Resultsmentioning

confidence: 99%

“…First, the symmetric C–O stretch is now much stronger than the asymmetric one, as expected for a M 2 (CO) 2 oscillator having almost parallel CO ligands . The second spectroscopic difference is unexpected: The 1 H and 13 C NMR spectra indicate that both MoCp(CO) fragments of the molecule are apparently equivalent, which is inconsistent with the asymmetric coordination of the propenylylidene ligand in this complex, and this situation remained the same on cooling the solution down to 183 K. We have previously encountered the same situation in related methoxy-substituted complex cis -[Mo 2 Cp 2 {μ-κ 2 :η 3 -C(OMe)CRCR}(μ-PCy 2 )(CO) 2 ] (R = CO 2 Me) and have interpreted it as resulting from a fluxional process whereby the central C atom of the hydrocarbon chain (C10 in Figure ) binds alternatively each of the Mo atoms, a rearrangement which yields, on the fast exchange limit, equivalent environments for the pairs of CO and Cp ligands.…”

Section: Resultsmentioning

confidence: 99%

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C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂] with Small Unsaturated Organics

et al. 2016

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The ability of the title compound to promote C–C coupling processes has been analyzed by examining its reactions with diazoalkanes, alkynes, and other unsaturated organic molecules. The title compound reacted with N2CPh2 at room temperature to give a mixture of ketenyl complex [Mo2Cp2{μ-κ1:η2-C(Ph)CO}(μ-PCy2)(CO)(κ1-N2CPh2)] and carbyne complex [Mo2Cp2(μ-CPh)(μ-PCy2)(CO)(κ1-N2CPh2)], products which can be converted into each other by addition/removal of CO, respectively. In contrast, denitrogenation took place rapidly in analogous reactions with diazomethane and benzylazide at room temperature, to yield, respectively, the corresponding alkenyl [Mo2Cp2{μ-κ1:η2-C(Ph)CH2}(μ-PCy2)(CO)2] and iminoacyl [Mo2Cp2{μ-C(Ph)NCH2Ph}(μ-PCy2)(CO)2] derivatives, following from selective C–C and C–N couplings. The title compound reacted at 333 K with methyl propiolate to give the corresponding propenylylidene derivative [Mo2Cp2{μ-κ2:η3-CPhCHC(CO2Me)}(μ-PCy2)(CO)2], as a result of selective coupling of the carbyne ligand to the terminal carbon of the alkyne. A related complex could be obtained when using the internal alkyne dimethyl acetylenedicarboxylate.

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Section: Resultssupporting

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂] with Small Unsaturated Organics

et al. 2016

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“…[196]. The 32-electron complex [Mo2Cp2(μ-COMe)(μ-PCy2)(CO)2] (Cp = η 5 -C5H5) reacts at 333 K with terminal alkynes RC≡CR to give the corresponding derivatives [Mo2Cp2{μ-κ 2 :η 3 -CRCHC(OMe)}(μ-PCy2)(CO)2], (R = p-tol, CO2Me), with good yields (Scheme 49) [197]. [198].…”

Section: Some Cluster Complexes Of G-6 Metal Carbonyl Complexesmentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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KEYWORDSThe special interest attached to the chemistry of metal carbonyls arises from several causes. While quite distinct from the metal carbonyls in the organometallic compounds, they differ in physical properties (e.g., their volatility) from all other compounds of the transition metals. Chemically, they constitute a group of compounds in which the formal valency of the metal atoms is zero, and in this respect (apart, perhaps, from the ammoniates of the alkali metals) they are comparable only with the recently discovered compounds. As a class, the carbonyls are reactive compounds, and a number of new types of inorganic compounds have been discovered. In the concepts for new products, performance, product safety, and product economy criteria are equally important. They are taken into account already when the raw material base for a new industrial product development is defined. Since the discovery of nickel carbonyl by Mond and Langer in 1888, the carbonyls of the iron group and of chromium, molybdenum and tungsten have found important technical applications, e.g., in the Mond nickel process, and for the preparation of the metals in a state of subdivision and of purity suitable for powder metallurgy, for catalysts, etc. The reaction mechanism of the processes developed for producing the carbonyls technically has only recently received its interpretations. Within the space of review it is necessary to limit discussion to a few topics. Particular stress has accordingly laid upon (a) the chemical bonding in metal carbonyls, (b) importance of IR and NMR spectroscopy in characterization of metal carbonyls, (c) substitution reactions of G-VIb metal carbonyls, (d) kinetics and mechanism of substitution reactions in metal carbonyls, (e) substituted complexes of G-VIb metal carbonyl, (f) chelate complexes of G-VIb metal carbonyls, (g) uses of G-VIb metal carbonyl complexes and (h) studies done on G-VIb metal carbonyls.

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“…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 C–C coupling processes involved in the FT synthesis. Indeed, our previous studies on the behavior of the unsaturated methoxycarbyne-bridged complexes [Mo 2 Cp 2 (μ-COMe)(μ-PCy 2 )(μ-CO)] and [Mo 2 Cp 2 (μ-COMe)(μ-PCy 2 )(CO) 2 ] revealed a high and multipositional reactivity of these electron-deficient dimetal centers under mild conditions, including some interesting C–C bond formation processes. , …”

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Multisite Reactivity of the Central Mo₂CP Core in the Unsaturated Carbyne-Bridged Complex [Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(CO)₂]

et al. 2011

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The title compound reacted with HBF4·OEt2 at room temperature to give a mixture of the agostic-like, phosphine-bridged complex [Mo2Cp2(μ-CPh)(μ-κ1: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 HCCCO2Me 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,κ:η,κ-C(Ph)Se}(μ-PCy2)(CO)2], respectively. In contrast, the addition of a neat donor at the metal site can induce a reversible carbyne–carbonyl coupling, as observed in the reaction with N2CPh2 to give the ketenyl derivative [Mo2Cp2{μ-η1:η2-C(Ph)CO}(μ-PCy2)(CO)(κ1-N2CPh2)].

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Alkyne to carbyne coupling reactions of the unsaturated methoxycarbyne-bridged complex [Mo2(η5-C5H5)2(μ-COMe)(μ-PCy2)(CO)2]

Cited by 6 publications

References 40 publications

C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂] with Small Unsaturated Organics

C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂] with Small Unsaturated Organics

The chemistry of group-VIb metal carbonyls

Multisite Reactivity of the Central Mo₂CP Core in the Unsaturated Carbyne-Bridged Complex [Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(CO)₂]

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Alkyne to carbyne coupling reactions of the unsaturated methoxycarbyne-bridged complex [Mo2(η5-C5H5)2(μ-COMe)(μ-PCy2)(CO)2]

Cited by 6 publications

References 40 publications

C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo2Cp2(μ-CPh)(μ-PCy2)(CO)2] with Small Unsaturated Organics

C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo2Cp2(μ-CPh)(μ-PCy2)(CO)2] with Small Unsaturated Organics

The chemistry of group-VIb metal carbonyls

Multisite Reactivity of the Central Mo2CP Core in the Unsaturated Carbyne-Bridged Complex [Mo2(η5-C5H5)2(μ-CPh)(μ-PCy2)(CO)2]

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C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂] with Small Unsaturated Organics

C–C and C–N Couplings in Reactions of the Benzylidyne-Bridged Complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(CO)₂] with Small Unsaturated Organics

Multisite Reactivity of the Central Mo₂CP Core in the Unsaturated Carbyne-Bridged Complex [Mo₂(η⁵-C₅H₅)₂(μ-CPh)(μ-PCy₂)(CO)₂]