TY - JOUR
T1 - Theoretical Study of Transition Metal Compounds with Molybdenum- and Tungsten-Phosphorus Triple Bonds
AU - Wagener, Thomas
AU - Frenking, Gernot
PY - 1998
Y1 - 1998
N2 - Quantum mechanical calculations at the HF, MP2, DFT (B3LYP), and CCSD(T) levels of theory using quasirelativistic effective core potentials for the metal and valence basis sets of DZP quality are reported for the transition metal complexes [M(P)(NH2)3] (1, 2), [M(PS)(NH2)3] (3, 4), [M(P)(NH2)3(NH3)] (5, 6), [M(P)(N3N)] (7, 8; N3N = [(HNCH2CH2)3N]3-), and [(M(PS)(NH2)3(NH3)] (9, 10) with M = Mo, W. The B3LYP-optimized geometries of 1-10 are in good agreement with experiment. Bond dissociation energies for the LnMP-S bonds calculated at B3LYP are 8-10 kcal/mol higher than the CCSD(T) values. The LnMP-S and M-NH3 bonds of 9 and 10 are predicted to be stronger than the respective bonds of 3-6. 31P NMR chemical shifts and the anisotropic components have been calculated using the IGLO and GIAO approaches. The results are in accord with experimental data. The bonding situation of the complexes has been analyzed with the help of the NBO partitioning scheme. The phosphide complexes LnMP have metal≡P triple bonds, while the phosphorus-sulfide complexes have LnM=P=S double bonds. This formally reduces the number of coordination sites at the metal, which explains the significantly shorter and stronger bond with an amine trans to the M=P=S moiety.
AB - Quantum mechanical calculations at the HF, MP2, DFT (B3LYP), and CCSD(T) levels of theory using quasirelativistic effective core potentials for the metal and valence basis sets of DZP quality are reported for the transition metal complexes [M(P)(NH2)3] (1, 2), [M(PS)(NH2)3] (3, 4), [M(P)(NH2)3(NH3)] (5, 6), [M(P)(N3N)] (7, 8; N3N = [(HNCH2CH2)3N]3-), and [(M(PS)(NH2)3(NH3)] (9, 10) with M = Mo, W. The B3LYP-optimized geometries of 1-10 are in good agreement with experiment. Bond dissociation energies for the LnMP-S bonds calculated at B3LYP are 8-10 kcal/mol higher than the CCSD(T) values. The LnMP-S and M-NH3 bonds of 9 and 10 are predicted to be stronger than the respective bonds of 3-6. 31P NMR chemical shifts and the anisotropic components have been calculated using the IGLO and GIAO approaches. The results are in accord with experimental data. The bonding situation of the complexes has been analyzed with the help of the NBO partitioning scheme. The phosphide complexes LnMP have metal≡P triple bonds, while the phosphorus-sulfide complexes have LnM=P=S double bonds. This formally reduces the number of coordination sites at the metal, which explains the significantly shorter and stronger bond with an amine trans to the M=P=S moiety.
UR - http://www.scopus.com/inward/record.url?scp=0000808262&partnerID=8YFLogxK
U2 - 10.1021/ic971139m
DO - 10.1021/ic971139m
M3 - 文章
AN - SCOPUS:0000808262
SN - 0020-1669
VL - 37
SP - 1805
EP - 1811
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 8
ER -