Six-coordinate Group 13 complexes: the role of d orbitals and electron-rich multi-center bonding.
Bonding in six-coordinate complexes based on Group 13 elements (B, Al, Ga, In, Tl) is usually considered to be identical to that in transition-metal analogues. We herein demonstrate through sophisticated electronic-structure analyses that the bonding in these Group 13 element complexes is fundamentally different and better characterized as electron-rich hypervalent bonding with essentially no role for the d orbitals. This characteristic is carried through to the molecular properties of the complex.
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628BL Delft (The Netherlands). M.G.Goesten@tue.nl.|Inorganic Materials Chemistry, Eindhoven University of Technology, P.O.Box 513, 5600 MB Eindhoven (The Netherlands). M.G.Goesten@tue.nl.
Maarten G
MG
Goesten
Department of Theoretical Chemistry, VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands).
Célia
C
Fonseca Guerra
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628BL Delft (The Netherlands).
Freek
F
Kapteijn
Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628BL Delft (The Netherlands).
Jorge
J
Gascon
Department of Theoretical Chemistry, VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands). F.M.Bickelhaupt@vu.nl.|Institute of Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (The Netherlands). F.M.Bickelhaupt@vu.nl.
F Matthias
FM
Bickelhaupt
bond theory; coordination modes; hypervalent compounds; main group chemistry; molecular orbital theory