Phosphorus-Sulfur Bond Cleavage at a Mixed-metal Centre; Reaction of 5-C5H5)> with PPh2(SPh)

DOI: 10.1039/DT9940003607

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3607 - 3614 (1994)

Update date:2022-08-30

Topics:

Authors:

Ingham, Scott L.

Mays, Martin J.

Raithby, Paul R.

Solan Gregory A.

Sundavadra, Bharat V.

et al. et al.

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Article abstract of DOI:10.1039/DT9940003607

The bimetallic cobalt-molybdenum complex <(OC)4CoMo(CO)3(η⁵-C5H5)> reacted with phenylacetylene in benzene to give the bimetallic alkyne-bridged complex <(OC)3Co(μ-PhCCH)Mo(CO)2(η⁵-C5H5)> 1 as the major product and the trimetallic alkylidyne-capped complex 3-CCH2Ph)(CO)8(η⁵=C5H5)> 2 as the minor product.Reaction of 1 with PPh2(SPh) resulted in substitution of a carbonyl group on the cobalt atom to give <<(PhS)Ph2P>(OC)2Co(μ-PhCCH)Mo(CO)2(η⁵-C5H5)> 3.Thermolysis of 3 in refluxing toluene afforded, as the major product, the complex <(η⁵-C5H5)(OC)Mo(μ-PPh2CH=CPh)(μ-SPh)Co(CO)2> 4, in which the unsymmetrical alkyne in 3 has been incorporated into a four-membered metallacycle, , such that the phenyl substituent is positioned on the carbon atom remote from the phosphide group.The related complex <(η⁵-C5H5)(OC)Mo(μ-PPh2CH=CPh)(μ-SPh)Co(CO)(PPh3)> 5, in which one of the carbonyl groups on the cobalt atom in 4 has been substituted by a triphenylphosphine ligand, has also been isolated as a minor product from this reaction.Conversion of 4 into 5 has been achieved separately by reaction of 4 with PPh3.Similarly, reaction of PPh2(SPh) with 4 yields a related compound <(η⁵-C5H5)(OC)Mo(μ-PPh2CH=CPh)(μ-SPh)Co(CO)> 6, in which the same carbonyl group on the cobalt atom has been substituted by PPh2(SPh).Single-crystal X-ray diffraction studies have been performed on complexes 2, 4 and 6.

Full text of DOI:10.1039/DT9940003607

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