Title

Synthesis of (η6-C13H10)Mn(CO)2LPF6 and (η6-C13Hg9)Mn(CO)2L complexes (L = phosphines and phosphites) and kinetic studies of η6 to η5 ring slippage reactions

Abstract

This report describes the syntheses and characterizations of (η6-C13H10)Mn(CO)2LPF6 and (η6-C13H9)Mn(CO)2L complexes (L = P(OEt)3, PPh3, PEt3, and η1-(diphos) (diphos = 1,2-bis(diphenylphosphino)ethane), and kinetic studies of (η6-C13H9)Mn(CO),L→(η5-C13H9)Mn(CO)2L ring slippage reactions. ΔH‡ values for the η6 → η5 slippage reactions of the P(OEt)3 (26.4 kcal/mol), PPh3 (23.1 kcal mol-1), and PEt3 (25.6 kcal/mol-1) complexes are similar to values previously reported for CO and P(n-Bu)3 complexes. The unusually low value of ΔH‡ = 19.9 kcal/mol for the η1-diphos complex is attributed to an intermediate stabilized by an intramolecular nucleophilic attack of the free end of the diphos ligand on the metal center.

Department(s)

Chemistry

Document Type

Article

DOI

https://doi.org/10.1016/0022-328X(94)87080-2

Keywords

Kinetic studies, Manganese, Phosphines, Phosphites, Ring slippage

Publication Date

8-23-1994

Journal Title

Journal of Organometallic Chemistry

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