Geometry and Electronic Structure of (CO)3NiCH2. A Model Transition-Metal Carbene

Dale Spangler; John J. Wendoloski; Michel Dupuis; Maynard M.L. Chen; Henry F. Schaefer

doi:10.1021/ja00404a004

Geometry and Electronic Structure of (CO)3NiCH2. A Model Transition-Metal Carbene

Dale Spangler, John J. Wendoloski, Michel Dupuis, Maynard M.L. Chen, Henry F. Schaefer

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

70 Citations (Scopus)

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
Pages (from-to)	3985-3990
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	103
Issue number	14
DOIs	https://doi.org/10.1021/ja00404a004
Publication status	Published - Jul 1981

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Spangler, D., Wendoloski, J. J., Dupuis, M., Chen, M. M. L., & Schaefer, H. F. (1981). Geometry and Electronic Structure of (CO)3NiCH2. A Model Transition-Metal Carbene. Journal of the American Chemical Society, 103(14), 3985-3990. https://doi.org/10.1021/ja00404a004

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title = "Geometry and Electronic Structure of (CO)3NiCH2. A Model Transition-Metal Carbene",

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 {\AA}, 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.",

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AU - Spangler, Dale

AU - Wendoloski, John J.

AU - Dupuis, Michel

AU - Chen, Maynard M.L.

AU - Schaefer, Henry F.

PY - 1981/7

Y1 - 1981/7

N2 - 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.

AB - 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.

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