TY - JOUR

T1 - Structure and internal rotation in quadruply bonded α-Mo2Cl4(P-P)2 complexes: A density functional theory study of the cis-Mo2Cl4(PH3)4 complex

AU - Demachy, Isabelle

AU - Jean, Yves

AU - Lledos, Agusti

PY - 1999/4/16

Y1 - 1999/4/16

N2 - The cis-Mo2Cl4(PH3)4 complex is used as a model for the α-isomer of the Mo2Cl4(P-P)2 complexes where P-P is a diphosphine ligand. Density functional theory calculations with the B3LYP functional are performed for the lowest singlet (δ2) and triplet (3δδ*) states. The eclipsed C2h conformation is found to be the most stable structure for both these electronic states, the singlet state being the electronic ground state. The singlet-triplet energy difference, which gives a measure of the δ-bond energy, is equal to 10.9 kcal/mol (spin-projected broken-symmetry calculations). A rotational barrier around the Mo-Mo bond of about 27 kcal/mol is found for both electronic states, the singlet state remaining the electronic ground state whatever the value of the internal rotational angle.

AB - The cis-Mo2Cl4(PH3)4 complex is used as a model for the α-isomer of the Mo2Cl4(P-P)2 complexes where P-P is a diphosphine ligand. Density functional theory calculations with the B3LYP functional are performed for the lowest singlet (δ2) and triplet (3δδ*) states. The eclipsed C2h conformation is found to be the most stable structure for both these electronic states, the singlet state being the electronic ground state. The singlet-triplet energy difference, which gives a measure of the δ-bond energy, is equal to 10.9 kcal/mol (spin-projected broken-symmetry calculations). A rotational barrier around the Mo-Mo bond of about 27 kcal/mol is found for both electronic states, the singlet state remaining the electronic ground state whatever the value of the internal rotational angle.

U2 - 10.1016/S0009-2614(99)00249-3

DO - 10.1016/S0009-2614(99)00249-3

M3 - Article

VL - 303

SP - 621

EP - 628

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 5-6

ER -