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

Research output: Contribution to journal › Article

69 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 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

Fingerprint

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 journal › Article

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 D, Wendoloski JJ, Dupuis M, Chen MML, Schaefer HF. Geometry and electronic structure of (CO)3NiCH2. A model transition-metal carbene. Journal of the American Chemical Society. 1981;103(14):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.
@article{7613991b778745a8b2db81f809fff79d,
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 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 {\AA}, 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.",
author = "Dale Spangler and Wendoloski, {John J.} and Michel Dupuis and Chen, {Maynard M L} and Schaefer, {Henry F.}",
year = "1981",
language = "English",
volume = "103",
pages = "3985--3990",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Geometry and electronic structure of (CO)3NiCH2. A model transition-metal carbene

AU - Spangler, Dale

AU - Wendoloski, John J.

AU - Dupuis, Michel

AU - Chen, Maynard M L

AU - Schaefer, Henry F.

PY - 1981

Y1 - 1981

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 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.

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 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.

UR - http://www.scopus.com/inward/record.url?scp=0007653901&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0007653901&partnerID=8YFLogxK

M3 - Article

VL - 103

SP - 3985

EP - 3990

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 14

ER -

Access to Document