Quadruple bonding of bare group-13 atoms in transition metal complexes. Issue 42 (8th October 2020)

• Record Type: Journal Article
• Authors: Pan, Sudip; Manoj, Sai; Frenking, Gernot
• Is Part Of: Dalton transactions. Volume 49:Issue 42(2020)
• Page Start: 14815
• Page End: 14825
• Publication Date: 2020-10-08
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt02773a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Bonding analysis shows that E–TM(CO)3 q bonds possess four bonding components: one strong electron-sharing σ bond E–TM(CO)3 q, two π backdonations E⇇TM(CO)3 q and one weak σ donation E→TM(CO)3 q . Abstract : Density functional theory calculations at the M06-D3/def2-TZVPPD level of the group-13 anion complexes EFe(CO)3 − (E = B–Tl) and the isoelectronic neutral and charged boron adducts BTM(CO)3 q (TM q = Fe −, Ru −, Os −, Co, Rh, Ir, Ni +, Pd +, Pt + ) give tetrahedral ( C 3v ) geometries in the 1 A1 electronic ground state as equilibrium structures. The analysis of the bonding situation with the energy decomposition analysis in combination with natural orbital for chemical valence method suggests that the E–TM(CO)3 q bonds possess four bonding components: (a) one strong electron-sharing σ bond E–TM(CO)3 q ; (b) two π backdonations E⇇TM(CO)3 q and (c) one weak σ donation E→TM(CO)3 q . The relative strength of the four bonding components depends on the charge of the system, the transition metal TM and the group-13 atom E. The σ donation E→TM(CO)3 q is in all systems rather weak while the associated charge migration is not negligible. A similar situation of the bonding of terminal group-13 atoms Ga and In is found in Ga–TM(GaCp)4 + and E–Pt(PMe3 )3 + (TM = Ni, Pd, Pt; E = Ga, In), which are model compounds for the stable complexes GaTM(GaCp*)4 + (TM = Ni, Pt) and InPt(PPh3 )3 + . The quadruple bonds E→TML2 are hybrids of electron-sharing and dative bonds.