Solvent and nucleophile effects on the carbonyl insertion reaction into metal-carbon bonds

Cotton J.D., Kroes M.M., Markwell R.D. and Miles E.A. (1990) Solvent and nucleophile effects on the carbonyl insertion reaction into metal-carbon bonds. Journal of Organometallic Chemistry, 388 1-2: 133-142. doi:10.1016/0022-328X(90)85355-3


Author Cotton J.D.
Kroes M.M.
Markwell R.D.
Miles E.A.
Title Solvent and nucleophile effects on the carbonyl insertion reaction into metal-carbon bonds
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)85355-3
Volume 388
Issue 1-2
Start page 133
End page 142
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 rate constant, k3, for the direct insertion of carbon monoxide induced by tertiary phosphines into [(η5-C5H5)(CO)3MoCH 2C6H5] in toluene solution decreases steadily with increasing cone angle of the phosphine. In contrast, for [(CO)5MnCH2C6H5], k3 increases with decrease in the Tolman electronic parameter, v, of the phosphine (i.e., with increasing electron donation) and does not correlate with the cone angle. However, k3 reflects the size of the phosphine to a greater degree as the size of the benzyl substituent on manganese increases. An analysis of k1 values in the solvent-assisted insertion pathway has been made for both the molybdenum and manganese systems in THF, 2-MeTHF and 2,5-Me2THF solutions. The general decrease in k1 with increasing size of the solvent for the cyclopentadienyl-molybdenum system becomes less marked as the size of the benzyl substituent increases. The manganese complexes are relatively less sensitive to solvent size. A comparison has been made between the nucleophilic role of a solvent molecule in the k1 step and that of a tertiary phosphine in the k3 step.
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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Created: Sat, 09 Jul 2016, 16:41:18 EST by System User