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Bonding Situation in “Early‐Late” Transition Metal Complexes Cl 3 M – M ′(PCl 3 ) 4 ( M = Ti, Zr, Hf; M ′ = Co, Rh, Ir) – Theoretical Study for a Ligand Fine Tuning of M – M ′ Bonds
Author(s) -
Takagi Nozomi,
Krapp Andreas,
Frenking Gernot
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201100198
Subject(s) - crystallography , transition metal , metal , bond dissociation energy , bipyramid , density functional theory , chemistry , dissociation (chemistry) , trigonal bipyramidal molecular geometry , bond length , computational chemistry , crystal structure , catalysis , biochemistry , organic chemistry
Density functional theory calculations using the BP86 functional in combination with triple‐ζ quality basis sets have been carried out for the “early‐late” transition metal complexes Cl 3 M – M ′(PCl 3 ) 4 ( M = Ti, Zr, Hf; M ′ = Co, Rh, Ir) and the derivatives R 3 M – M ′L 4 ( R = Cl, NH 2 ; L = PCl 3 , PH 3 , CO). The calculations demonstrate that the metal–metal bond strength in R 3 M – M ′L 4 can be strongly influenced by the nature of the ligands R and L. The intrinsic interaction energy Δ E int and the bond dissociation energy of the M – M ′ bonds in Cl 3 M – M ′(PCl 3 ) 4 are much smaller than in the previously investigated species (H 2 N) 3 M – M ′(CO) 4 . The M – M ′ bonds become stronger in both sets of compounds when the metal atoms become heavier. The equilibrium geometries of Cl 3 M – M ′(PCl 3 ) 4 which have bipyramidal structures have C 3 symmetry. The M –Co bonds in Cl 3 Zr–Co(PCl 3 ) 4 and Cl 3 Hf–Co(PCl 3 ) 4 and to a lesser degree in Cl 3 Ti–Co(PCl 3 ) 4 are unusually long because of direct interactions between the equatorial PCl 3 groups and the group 4 atoms Zr, Hf. The analysis of the metal–metal interactions suggests that Cl 3 M – M ′(PCl 3 ) 4 has M – M ′ single bonds.