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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 1: Parent Compounds
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.200900791
Subject(s) - chemistry , natural bond orbital , bond dissociation energy , crystallography , transition metal , bond order , dissociation (chemistry) , density functional theory , sigma bond , bond length , valence (chemistry) , acceptor , chemical bond , single bond , bond energy , metal , computational chemistry , molecule , crystal structure , catalysis , group (periodic table) , biochemistry , physics , organic chemistry , condensed matter physics
The equilibrium geometries and bond dissociation energies of 16‐valence‐electron(VE) complexes [(PMe 3 ) 2 Cl 2 M(E)] and 18‐VE complexes [(PMe 3 ) 2 (CO) 2 M(E)] with M=Fe, Ru, Os and E=C, Si, Ge, Sn were calculated by using density functional theory at the BP86/TZ2P level. The nature of the ME bond was analyzed with the NBO charge decomposition analysis and the EDA energy‐decomposition analysis. The theoretical results predict that the heavier Group 14 complexes [(PMe 3 ) 2 Cl 2 M(E)] and [(PMe 3 ) 2 (CO) 2 M(E)] with E=Si, Ge, Sn have C 2 v equilibrium geometries in which the PMe 3 ligands are in the axial positions. The complexes have strong ME bonds which are slightly stronger in the 16‐VE species 1ME than in the 18‐VE complexes 2ME . The calculated bond dissociation energies show that the ME bonds become weaker in both series in the order C>Si>Ge>Sn; the bond strength increases in the order Fe