Substituent effects on the alkyl migration reaction in pentacarbonylbenzylmanganese(I) systems

Cotton J.D. and Markwell R.D. (1990) Substituent effects on the alkyl migration reaction in pentacarbonylbenzylmanganese(I) systems. Journal of Organometallic Chemistry, 388 1-2: 123-132. doi:10.1016/0022-328X(90)85354-2


Author Cotton J.D.
Markwell R.D.
Title Substituent effects on the alkyl migration reaction in pentacarbonylbenzylmanganese(I) systems
Journal name Journal of Organometallic Chemistry   Check publisher's open access policy
ISSN 0022-328X
Publication date 1990-05-15
Sub-type Article (original research)
DOI 10.1016/0022-328X(90)85354-2
Volume 388
Issue 1-2
Start page 123
End page 132
Total pages 10
Subject 1303 Specialist Studies in Education
1501 Accounting, Auditing and Accountability
1604 Human Geography
1605 Policy and Administration
1606 Political Science
2501 Materials Science (miscellaneous)
2505 Materials Chemistry
Abstract The k1 step of the formal insertion of carbon monoxide into a MnC σ bond in the reaction of substituted benzylmanganese complexes, [(CO)5MnCH2C6H5-nXn], with tertiary phosphines in acetonitrile is enhanced by electron-donating substituents in meta- and para-positions. Ortho-substitution by a methyl group causes a reduction in k1 compared with para-methyl substitution but di-substitution and single ortho-substitution by large alkyl groups increases reactivity. Similar behaviour occurs with Cl, F and CF3 as ortho-substituents. The value of k-1/k2, which reflects 1/k2, increases with increasing cone angle of the tertiary phosphine but the strongly basic phosphine, PCy3, although unreactive towards [(η5-C5H5)(CO)3MoR] and [(η5-C5H5)(CO)2FeR], induces insertion. Steric influences on the cis/trans isomerisation of the acyl product and its decarbonylation are discussed. Direct insertion of CO is observed for 2,4,6-triisopropyl- and 2,4,6-trimethyl-benzylmanganese complexes.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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