title: Carbonyl analogues? Analysis of Fe-E (E=B, Al, Ga) bonding in cationic terminal diyl complexes by density functional theory.
abstract: A series of DFT calculations has been carried out with the aim of characterizing the metal-group 13 element interaction in the novel cationic borylene complex [(eta5-C2Me5)Fe(CO)2(BMes)]+ (1) and related species of the type [eta5-C5R5)M(L)2(EX)]n+. In addition, comparisons have been made with charge neutral borylene complexes and with related group 14 based ligand systems (e.g. cationic metal carbonyls, carbenes and vinylidenes) for which models of bonding have previously been established. In this regard particular attention has been focused on the interpretation of (i) molecular orbital composition; (ii) bond dissociation energies (BDEs) and the ratio of ionic to covalent contributions (DeltaEelstat/DeltaEorb); and (iii) sigma and pi symmetry covalent contributions. The molecular orbital compositions for the prototype borylene complex 1 and for related cationic and neutral systems [e.g.[(eta5-C5H5)Fe(PMe3)2(BMes)]+ and (eta5-C5H5)Mn(CO2(BMes)]] are consistent with the presence of bonding interactions between metal and borylene fragments of both sigma and pi symmetry. Furthermore, on the basis of BDEs, DeltaEorb values and sigma/pi covalent ratios, the bonding in cationic terminal borylene complexes such as 1 appears to have as much right to be termed a M=E double bond as does that in archetypal Fischer carbene and related complexes such as [(eta5-C5R5)Fe(CO)2(CCMe2)]+ and [(eta5-C5R5)Fe(CO)2(CH2)]+.
authors.affiliation: Centre for Fundamental and Applied Main Group Chemistry, School of Chemistry, Cardiff University, PO Box 912, Park Place, Cardiff, UKCF10 3TB. AldridgeS@cardiff.ac.uk
authors.forename: Simon
authors.initials: S
authors.lastname: Aldridge
authors.forename: Andrea
authors.initials: A
authors.lastname: Rossin
authors.forename: Deborah L
authors.initials: DL
authors.lastname: Coombs
authors.forename: David J
authors.initials: DJ
authors.lastname: Willock