Affiliation:
1. Department of Chemistry and Biochemistry University of Windsor 401 Sunset Avenue Windsor ON, N9B 3P4 Canada
2. Department of Chemistry Western University 1151 Richmond Street London ON, N6A 3K7 Canada
Abstract
AbstractIn developing homogenous catalysts capable of CO2 activation, interaction with a metal center is often imperative. This work provides primary efforts towards the cooperative activation of CO2 using a Lewis acidic secondary coordination sphere (SCS) and iron via a paired theoretical/experimental approach. Specifically, this study reports efforts towards [Fe(diphosphine)2(N2)] as a CO2‐coordinated synthon where diphosphine=1,2‐bis(di(3‐cyclohexylboranyl)propylphosphino)ethane) (P2BCy4) or its precursor, 1,2‐bis(diallylphosphino)ethane (tape). Initial efforts toward the {Fe(0)‐N2} complex were focused on deprotonation reactions of [Fe(diphosphine)2(H)(NCCH3)]+ and reduction of [Fe(tape)2Cl2]. In the latter case, a mixture of intramolecularly π‐bonded alkene and associated metallacyclic Fe(II)—H species were produced – heating this mixture provided the hydride as the major product. Notably, the interconversion of this pair counters that of related intermolecular reactions between [Fe(depe)2] (depe=1,2‐bis(diethylphosphino)ethane) and ethylene, where hydride formation occurs subsequent to π‐coordination; this has been probed by theoretical calculations. Finally, reactivity of the metallacyclic {Fe(II)—H} complex with CO2 was probed, resulting in a pair of isomeric ferra(II)lactones.
Funder
Natural Sciences and Engineering Research Council of Canada
Subject
General Chemistry,Catalysis,Organic Chemistry