TY - JOUR
T1 - Phosphorus-sulfur bond cleavage at a mixed-metal centre; Reaction of [(OC)3Co(μ-PhCCH)Mo(CO)2(η5-C 5H5)] with PPh2(SPh)
AU - Ingham, Scott L.
AU - Mays, Martin J.
AU - Raithby, Paul R.
AU - Solan, Gregory A.
AU - Sundavadra, Bharat V.
AU - Conole, Gráainne
AU - Kessler, Margarlith
PY - 1994
Y1 - 1994
N2 - The bimetallic cobalt-molybdenum complex [(OC)4CoMo(CO)3(η5-C5H 5)] reacted with phenylacetylene in benzene to give the bimetallic alkyne-bridged complex [(OC)3Co(μ-PhCCH)Mo(CO)2(η5-C 5H5)] 1 as the major product and the trimetallic alkylidyne-capped complex [Co2Mo(μ3-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-PPh 2CH=CPh)(μ-SPh)Co(CO)2] 4, in which the unsymmetrical alkyne in 3 has been incorporated into a four- membered metallacycle, Mo-PPh2-CH-CPh, such that the phenyl substituent is positioned on the carbon atom remote from the phosphide group. The related complex [(η5-C5H5)(OC)Mo(μ-PPh 2CH=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-PPh 2CH=CPh)(μ-SPh)Co(CO){PPh2(SPh)}] 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.
AB - The bimetallic cobalt-molybdenum complex [(OC)4CoMo(CO)3(η5-C5H 5)] reacted with phenylacetylene in benzene to give the bimetallic alkyne-bridged complex [(OC)3Co(μ-PhCCH)Mo(CO)2(η5-C 5H5)] 1 as the major product and the trimetallic alkylidyne-capped complex [Co2Mo(μ3-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-PPh 2CH=CPh)(μ-SPh)Co(CO)2] 4, in which the unsymmetrical alkyne in 3 has been incorporated into a four- membered metallacycle, Mo-PPh2-CH-CPh, such that the phenyl substituent is positioned on the carbon atom remote from the phosphide group. The related complex [(η5-C5H5)(OC)Mo(μ-PPh 2CH=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-PPh 2CH=CPh)(μ-SPh)Co(CO){PPh2(SPh)}] 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.
UR - http://www.scopus.com/inward/record.url?scp=37049087854&partnerID=8YFLogxK
U2 - 10.1039/DT9940003607
DO - 10.1039/DT9940003607
M3 - Article
AN - SCOPUS:37049087854
SN - 1472-7773
SP - 3607
EP - 3614
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 24
ER -