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Reactions of P2Ph4 with Alkyne-bridged Dicobalt Carbonyl Complexes: Crystal Structures of (μ-P2Ph4)(CO)4>, (μ-PPh2)(CO)4> and (μ-PPh2)(CO)3(PPh3)>

DOI: 10.1039/DT9910003103

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3103 - 3114 (1991)

Update date:2022-08-05

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Authors:

Caffyn, Andrew J.Caffyn, Andrew J.

Mays, Martin J.Mays, Martin J.

Solan, Gregory A.Solan, Gregory A.

Braga, DarioBraga, Dario

Sabatino, PieraSabatino, Piera

et al.et al.

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Article abstract of DOI:10.1039/DT9910003103

The reactions of P2Ph4 with a variety of substituted alkyne complexes CR')(CO)6> in toluene give the complexes CR')(CO)5(P2Ph4)> 1 (R = R' = CO2Me 1a or Ph 1b; R = Ph, R' = H 1c and CR')(μ-P2Ph4)(CO)4> 2 (R = R' = Ph 2b; R = Ph, R' = H 2c.All three derivatives of type 1 are cleanly converted into 2 on thermolysis.An X-ray diffraction study of 2a reveals a square-planar Co2P2 core with the symmetrical alkyne perpendicular to the Co-Co bond.Further thermolysis of complexes 2 produces 3 (R = R' = CO2Me 3a or Ph 3b and (μ-PPh2)(CO)4> 4c (R = H, R' = Ph).The structure of 4c has been determined by X-ray analysis.The PPh2CHCPhC(O) ligand forms a five-membered metallacyclic ring incorporating one Co atom and is ?-bonded to the other Co atom.Complexes 3a and 3b are partially converted into 4a (R = R' = CO2Me) and 4b (R = R' = Ph) on treatment with CO.This reaction is reversed by heating 4a and 4b in solution or, more slowly, on standing at room temperature.The parent acetylene complex CH)(CO)6> reacts with P2Ph4 differently from the substituted derivatives to give as the principal product (μ-PPh2)(CO)4> 5d.The structure of the PPh3 derivative of this complex, (μ-PPh2)(CO)3(PPh3)> 6d, has been determined by X-ray diffraction.

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