Bis(carbonyl-κC)(N,N-dimethylthiocarbamoyl-κ2C,S)(pyridine-2-thiolato-κ2N,S)(triphenylphosphine-κP)molybdenum(II)

The successive treatment of [W(CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with n BuLi and ClPPh2 affords the phosphinocarbyne complex [W(CPPh2)(CO)2(Tp*)] (1), DFT interrogation of which suggests that reactions with electrophiles may involve both the phosphorus atom and/or the metal–carbon multiple bond. This is borne out in reactions of 1 with a variety of electrophilic reagents. With iodomethane or dimethylsulfide borane, electrophilic attack occurs exclusively at phosphorus to afford the compounds [W(CPMePh2)(CO)2(Tp*)]I ([2]I) and [W{CP(BH3)Ph2}(CO)2(Tp*)] (3). The reaction of 1 with sulfur affords both the thiophosphorylcarbyne complex [W{CP(S)Ph2}(CO)2(Tp*)] (4) and the thioacyl complex [W{η2-SCP(S)Ph2}(CO)2(Tp*)] (5), though 4 fails to react with sulfur to provide 5. In a similar manner, the complexes 2 and 3 also fail to react with sulfur, indicating that increasing the valance of the phosphorus center of 1 deactivates the WC bond toward further attack. Addition of selenium to 1 occurs exclusively at phosphorus to afford [W{CP(Se)Ph2}(CO)2(Tp*)] (6) with no indication of selenoacyl formation. Reversible protonation of 1 with HBF4 in diethyl ether precipitates the phosphoniocarbyne salt [W(CPHPh2)(CO)2(Tp*)]BF4, [8]BF4, which, however, on dissolution in dichloromethane rearranges irreversibly to the thermodynamic (ΔG cacld = 22.4 kJmol–1) phosphinocarbene isomer [W(η2CHPPh2)(CO)2(Tp*)]BF4, [9]BF4.

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Dicarbonylchlorido(phenoxythiocarbonyl-κ²C,S)bis(triphenylphosphane-κP)molybdenum(II)

Lee

Wang

Yih

et al. 2010

Acta Cryst E

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In the title complex, [Mo(C7H5OS)Cl(C18H15P)2(CO)2], the geometry around the metal atom is a capped octahedron. The phenoxythiocarbonyl ligand coordinates the MoII atom through the C and S atoms. A one-dimensional structure is formed by π–π intermolecular interactions and a supramolecular aggregation is determined by intermolecular C—H⋯O, C—H⋯Cl, C—H⋯π(arene) hydrogen bonds and CO⋯π(arene) interactions [O⋯centroid distances = 3.485 (4) and 3.722 (3) Å].

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Bis(carbonyl-κC)(N,N-dimethylthiocarbamoyl-κ²C,S)(pyridine-2-thiolato-κ²N,S)(triphenylphosphine-κP)molybdenum(II)

Cited by 3 publications

References 12 publications

Molybdenum

Molybdenum

Synthesis and Reactivity of Phosphinocarbyne Complexes

Dicarbonylchlorido(phenoxythiocarbonyl-κ²C,S)bis(triphenylphosphane-κP)molybdenum(II)

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Bis(carbonyl-κC)(N,N-dimethylthiocarbamoyl-κ2C,S)(pyridine-2-thiolato-κ2N,S)(triphenylphosphine-κP)molybdenum(II)

Cited by 3 publications

References 12 publications

Molybdenum

Molybdenum

Synthesis and Reactivity of Phosphinocarbyne Complexes

Dicarbonylchlorido(phenoxythiocarbonyl-κ2C,S)bis(triphenylphosphane-κP)molybdenum(II)

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Bis(carbonyl-κC)(N,N-dimethylthiocarbamoyl-κ²C,S)(pyridine-2-thiolato-κ²N,S)(triphenylphosphine-κP)molybdenum(II)

Dicarbonylchlorido(phenoxythiocarbonyl-κ²C,S)bis(triphenylphosphane-κP)molybdenum(II)