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Transition‐Metal Complexes [(PMe 3 ) 2 Cl 2 M(E)] and [(PMe 3 ) 2 (CO) 2 M(E)] with Naked Group 14 Atoms (E=C–Sn) as Ligands; Part 2: Complexation with W(CO) 5
Author(s) -
Parameswaran Pattiyil,
Frenking Gernot
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200900792
Subject(s) - chemistry , crystallography , bond dissociation energy , ligand (biochemistry) , transition metal , adduct , density functional theory , dissociation (chemistry) , metal , valence (chemistry) , stereochemistry , computational chemistry , biochemistry , receptor , organic chemistry , catalysis
Density functional calculations at the BP86/TZ2P level were carried out to understand the ligand properties of the 16‐valence‐electron(VE) Group 14 complexes [(PMe 3 ) 2 Cl 2 M(E)] ( 1ME ) and the 18‐VE Group 14 complexes [(PMe 3 ) 2 (CO) 2 M(E)] ( 2ME ; M=Fe, Ru, Os; E=C, Si, Ge, Sn) in complexation with W(CO) 5 . Calculations were also carried out for the complexes (CO) 5 W–EO. The complexes [(PMe 3 ) 2 Cl 2 M(E)] and [(PMe 3 ) 2 (CO) 2 M(E)] bind strongly to W(CO) 5 yielding the adducts 1ME–W(CO) 5 and 2ME–W(CO) 5 , which have C 2 v equilibrium geometries. The bond strengths of the heavier Group 14 ligands 1ME (E=Si–Sn) are uniformly larger, by about 6–7 kcal mol −1 , than those of the respective EO ligand in (CO) 5 W‐EO, while the carbon complexes 1MC–W(CO) 5 have comparable bond dissociation energies (BDE) to CO. The heavier 18‐VE ligands 2ME (E=Si–Sn) are about 23–25 kcal mol −1 more strongly bonded than the associated EO ligand, while the BDE of 2MC is about 17–21 kcal mol −1 larger than that of CO. Analysis of the bonding with an energy‐decomposition scheme reveals that 1ME is isolobal with EO and that the nature of the bonding in 1ME–W(CO) 5 is very similar to that in (CO) 5 W–EO. The ligands 1ME are slightly weaker π acceptors than EO while the π‐acceptor strength of 2ME is even lower.