TY - JOUR
T1 - Transition-metal complexes [(PMe3)2Cl 2M(E)] and [(PMe3)2(CO)2M(E)] with naked group 14 atoms (E = C-Sn) as ligands; part 2
T2 - complexation with W(CO) 5
AU - Parameswaran, Pattiyil
AU - Frenking, Gemot
PY - 2009/9/7
Y1 - 2009/9/7
N2 - 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 [(PMe3)2Cl2M(E)] (IME) and the 18-VE Group 14 complexes [(PMe3)2(CO)2M(E)] (2ME; M = Fe, Ru, Os; E = C, Si, Ge, Sn) in complexation with W(CO) 2. Calculations were also carried out for the complexes (CO)5W-EO. The complexes [(PMe3)2Cl2M(E)] and [(PMe3) 2(CO)2M(E)] bind strongly to W(CO)5 yielding the adducts IMEW(CO)5 and 2ME-W(CO)5, which have C 2v equilibrium geometries. The bond strengths of the heavier Group 14 ligands IME (E = Si-Sn) are uniformly larger, by about 6-7 kcal mol-1, than those of the respective EO ligand in (CO)5W-EO, while the carbon complexes IMC-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 IME-W(CO)5 is very similar to that in (CO)5W-EO. The ligands 1IME are slightly weaker jt acceptors than EO while the Jt-acceptor strength of 2ME is even lower.
AB - 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 [(PMe3)2Cl2M(E)] (IME) and the 18-VE Group 14 complexes [(PMe3)2(CO)2M(E)] (2ME; M = Fe, Ru, Os; E = C, Si, Ge, Sn) in complexation with W(CO) 2. Calculations were also carried out for the complexes (CO)5W-EO. The complexes [(PMe3)2Cl2M(E)] and [(PMe3) 2(CO)2M(E)] bind strongly to W(CO)5 yielding the adducts IMEW(CO)5 and 2ME-W(CO)5, which have C 2v equilibrium geometries. The bond strengths of the heavier Group 14 ligands IME (E = Si-Sn) are uniformly larger, by about 6-7 kcal mol-1, than those of the respective EO ligand in (CO)5W-EO, while the carbon complexes IMC-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 IME-W(CO)5 is very similar to that in (CO)5W-EO. The ligands 1IME are slightly weaker jt acceptors than EO while the Jt-acceptor strength of 2ME is even lower.
KW - Bonding analysis
KW - Density functional calculations
KW - Group 14 elements
KW - Isolobal relationship
KW - Transition metals
UR - http://www.scopus.com/inward/record.url?scp=69749085463&partnerID=8YFLogxK
U2 - 10.1002/chem.200900792
DO - 10.1002/chem.200900792
M3 - 文章
AN - SCOPUS:69749085463
SN - 0947-6539
VL - 15
SP - 8817
EP - 8824
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 35
ER -