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)

Avelino Martín; Martin J. Mays; Paul R. Raithby; Gregory A. Solan

doi:10.1039/DT9930001431

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)

Avelino Martín
, Martin J. Mays
, Paul R. Raithby
, Gregory A. Solan

University of Cambridge

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	1431-1439
Number of pages	9
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	9
DOIs	https://doi.org/10.1039/DT9930001431
Publication status	Published - 1993

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General Chemistry

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@article{556d1ee81eac4bd6baff792d36b83d4e,

title = "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)",

abstract = "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.",

author = "Avelino Mart{\'i}n and Mays, \{Martin J.\} and Raithby, \{Paul R.\} and Solan, \{Gregory A.\}",

year = "1993",

doi = "10.1039/DT9930001431",

language = "English",

pages = "1431--1439",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "9",

}

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 - https://www.scopus.com/pages/publications/37049085564

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 -

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)

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