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

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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 11p 6d/11s 8p 3d), C,O(9s 5p/4s 2p), H(5s/3s). The critical predicted equilibrium geometrical parameters were R[Ni-C(methylene)] = 1.83 Å, θ(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 languageEnglish
Pages (from-to)3985-3990
Number of pages6
JournalJournal of the American Chemical Society
Volume103
Issue number14
Publication statusPublished - 1981

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Coordination Complexes
Molecular Structure
Nickel
Electronic structure
Transition metals
Metals
Molecular electronics
Geometry
Metal complexes
Molecular structure
Molecules
carbene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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.

Geometry and electronic structure of (CO)3NiCH2. A model transition-metal carbene. / Spangler, Dale; Wendoloski, John J.; Dupuis, Michel; Chen, Maynard M L; Schaefer, Henry F.

In: Journal of the American Chemical Society, Vol. 103, No. 14, 1981, p. 3985-3990.

Research output: Contribution to journalArticle

Spangler, D, Wendoloski, JJ, Dupuis, M, Chen, MML & Schaefer, HF 1981, 'Geometry and electronic structure of (CO)3NiCH2. A model transition-metal carbene', Journal of the American Chemical Society, vol. 103, no. 14, pp. 3985-3990.
Spangler, Dale ; Wendoloski, John J. ; Dupuis, Michel ; Chen, Maynard M L ; Schaefer, Henry F. / Geometry and electronic structure of (CO)3NiCH2. A model transition-metal carbene. In: Journal of the American Chemical Society. 1981 ; Vol. 103, No. 14. pp. 3985-3990.
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