Abstract
The first application of nonempirical molecular electronic structure theory to a realistic transition-metal carbene complex is reported. The system chosen was (CO)3NiCH2, methylene(tricarbonyl)nickel(0). All studies were carried out at the self-consistent-field (SCF) level. A large and flexibly contracted basis set was chosen, labeled Ni(15s lip 6d/l Is 8p 3d), C,0(9s 5p/4s 2p), H(5s/3s). The critical predicted equilibrium geometrical parameters were R[Ni-C(methylene)] = 1.83 Å, 0(HCH) = 108°. The sixfold barrier to rotation about the Ni-C(methylene) axis is small, ~0.2 kcal. The electronic structure of (CO)3NiCH2 is discussed and compared with those of the “naked” complex NiCH2 and the stable Ni(CO)4 molecule.
Original language | English |
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Pages (from-to) | 3985-3990 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 103 |
Issue number | 14 |
DOIs | |
Publication status | Published - Jul 1981 |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry