TY - JOUR
T1 - Reactions of the heteronuclear alkyne-bridged cobalt-molybdenum complex [(OC)3Co{μ-C2(CO2Me)2}Mo(CO) 2(η5-C5H5)] with PPh2H, P2Ph4 and PPh2(SPh)
AU - Martín, Avelino
AU - Mays, Martin J.
AU - Raithby, Paul R.
AU - Solan, Gregory A.
PY - 1993
Y1 - 1993
N2 - The complex [(OC)3Co{μ-C2(CO2Me)2}Mo(CO) 2(η5-C5H5)] 1 reacts preferentially at the Co atom with PPh2H, P2Ph4 and PPh2(SPh) to give initially the mono-substituted products [L(OC)2Co{μ-C2(CO2Me) 2}Mo(CO)2(η5-C5H5)] [L = PPh2H 2, P2Ph4 3 or PPh2(SPh) 4]. In the case of PPh2H further reaction takes place at the Mo atom to give the bis-substituted product [(HPh2P)(OC)2Co{μ-C2(CO2Me) 2}Mo(CO)(η5-C5H5)(PPh 2H)] 5. Thermolysis of the substituted derivatives 2-5 results in either P-H, P-P or P-S bond cleavage. Thus for 2, the isomeric species [(η5-C5H5)(OC)Mo{μ-C(CO 2Me)=CH(CO2Me)}(μ-PPh2)Co(CO)2] 6 and [(OC)2Co{μ-C(CO2Me)=CH(CO2Me)}(μ-PPh 2)Mo(CO)(η5-C5H5)] 7 are obtained, whereas 3 gives [(OC)2Co{μ-PPh2C(CO2Me)=C(CO 2Me)}(μ-PPh2)Mo(CO)(η5-C 5H5)] 8, in which the Co atom is incorporated into a four-membered metallacycle. Thermolysis of 4 gives [(η5-C5H5)(OC)Mo{μ-PPh 2C(CO2Me)=C(CO2Me)}(μ-SPh)Co(CO) 2] 9 (in which the Mo atom is incorporated into a four-membered metallacycle) and thermolysis of 5 gives [(η5-C5H5)(OC)Mo{μ-C(CO 2Me)=CH(CO2Me)}(μ-PPh2)Co(CO)(PPh 2H)] 10. Complex 6 can be converted to 10 by reaction with PPh2H. The crystal structures of compounds 6 and 8 have been determined.
AB - The complex [(OC)3Co{μ-C2(CO2Me)2}Mo(CO) 2(η5-C5H5)] 1 reacts preferentially at the Co atom with PPh2H, P2Ph4 and PPh2(SPh) to give initially the mono-substituted products [L(OC)2Co{μ-C2(CO2Me) 2}Mo(CO)2(η5-C5H5)] [L = PPh2H 2, P2Ph4 3 or PPh2(SPh) 4]. In the case of PPh2H further reaction takes place at the Mo atom to give the bis-substituted product [(HPh2P)(OC)2Co{μ-C2(CO2Me) 2}Mo(CO)(η5-C5H5)(PPh 2H)] 5. Thermolysis of the substituted derivatives 2-5 results in either P-H, P-P or P-S bond cleavage. Thus for 2, the isomeric species [(η5-C5H5)(OC)Mo{μ-C(CO 2Me)=CH(CO2Me)}(μ-PPh2)Co(CO)2] 6 and [(OC)2Co{μ-C(CO2Me)=CH(CO2Me)}(μ-PPh 2)Mo(CO)(η5-C5H5)] 7 are obtained, whereas 3 gives [(OC)2Co{μ-PPh2C(CO2Me)=C(CO 2Me)}(μ-PPh2)Mo(CO)(η5-C 5H5)] 8, in which the Co atom is incorporated into a four-membered metallacycle. Thermolysis of 4 gives [(η5-C5H5)(OC)Mo{μ-PPh 2C(CO2Me)=C(CO2Me)}(μ-SPh)Co(CO) 2] 9 (in which the Mo atom is incorporated into a four-membered metallacycle) and thermolysis of 5 gives [(η5-C5H5)(OC)Mo{μ-C(CO 2Me)=CH(CO2Me)}(μ-PPh2)Co(CO)(PPh 2H)] 10. Complex 6 can be converted to 10 by reaction with PPh2H. The crystal structures of compounds 6 and 8 have been determined.
UR - http://www.scopus.com/inward/record.url?scp=37049085564&partnerID=8YFLogxK
U2 - 10.1039/DT9930001431
DO - 10.1039/DT9930001431
M3 - Article
AN - SCOPUS:37049085564
SN - 1472-7773
SP - 1431
EP - 1439
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 9
ER -