Dicarbonylchlorido(phenoxythiocarbonyl-κ2C,S)bis(triphenylphosphane-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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Synthesis and Reactivity of Phosphinocarbyne Complexes

Colebatch

Hill

Sharma

2014

Organometallics

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

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Synthesis and Reactivity of Phosphinocarbyne Complexes

Synthesis and Reactivity of Phosphinocarbyne Complexes

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