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Electronic structures of tetragonal nitrido and nitrosyl metal complexes

Hummel, Patrick and Winkler, Jay R. and Gray, Harry B. (2008) Electronic structures of tetragonal nitrido and nitrosyl metal complexes. Theoretical Chemistry Accounts, 119 (1-3). pp. 35-38. ISSN 1432-881X. doi:10.1007/s00214-006-0236-8.

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The standard oxidation states of central metal atoms in C_(4v) nitrido ([M(N)(L)₅]^z) complexes are four units higher than those in corresponding nitrosyls ([M(NO)(L)₅]^z) (L=CN: z = 3−, M = Mn, Tc, Re; z = 2−, M = Fe, Ru, Os; L = NH₃: z = 2+, M = Mn, Tc, Re; z = 3+, M = Fe, Ru, Os). Recent work has suggested that [Mn(NO)(CN)₅]³⁻ behaves electronically much closer to Mn(V)[b₂(xy)]², the ground state of [Mn(N)(CN)₅]³⁻, than to Mn(I)[b₂(xy)]²[e(xz,yz)]⁴. We have employed density functional theory and time-dependent density functional theory to calculate the properties of the ground states and lowest-lying excitations of [M(N)(L)₅]^z and [M(NO)(L)₅]^z . Our results show that [M(N)(L)₅]^z and [M(NO)(L)₅]^z complexes with the same z value have strikingly similar electronic structures.

Item Type:Article
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URLURL TypeDescription ReadCube access
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2007 Springer-Verlag. Received: 13 August 2006; Accepted: 8 November 2006; Published online: 12 January 2007. This paper is dedicated to Philip Stephens in appreciation of his deep and lasting contributions to molecular spectroscopy. The work was supported by the National Science Foundation and the Arnold and Mabel Beckman Foundation.
Funding AgencyGrant Number
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:Density functional theory; Time dependent density functional theory; Electronic structures; Nitrido; Nitric oxide
Issue or Number:1-3
Record Number:CaltechAUTHORS:20200212-153542105
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Official Citation:Hummel, P., Winkler, J.R. & Gray, H.B. Theor Chem Account (2008) 119: 35.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:101256
Deposited By: Tony Diaz
Deposited On:12 Feb 2020 23:47
Last Modified:16 Nov 2021 18:01

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