Kinetics of nucleophilic addition of tertiary phosphines to dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation

David M. Birney, Annette M. Crane, D. A. Sweigart

Research output: Contribution to journalArticle

23 Scopus citations

Abstract

Tertiary phosphines rapidly add to the ring in dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation to form phosphonium adducts. Kinetic studies of this reaction support a mechanism consisting of direct bimolecular attack on the ring. Reactivity towards nucleophilic attack by phosphines follows the order: [(C7H8)Mn(CO)3]+ > [(C4H4)Fe(CO)2NO]+ > [(C6H7)Fe(CO)3]+ > [(C6H6OMe)Fe(CO)3]+ ≳ [(C7H7)M(CO)3]+ (M = Cr, Mo, W) > [(C6H6)Mn(CO)3]+. Coordinated cycloheptatriene is about 104 times more electrophilic towards phosphine nucleophiles than is coordinated benzene.

Original languageEnglish
Pages (from-to)187-192
Number of pages6
JournalJournal of Organometallic Chemistry
Volume152
Issue number2
DOIs
StatePublished - May 30 1978

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