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Electronic Structures of Nitridomanganese(V) Complexes

Chang, Christopher J. and Connick, William B. and Low, Donald W. and Day, Michael W. and Gray, Harry B. (1998) Electronic Structures of Nitridomanganese(V) Complexes. Inorganic Chemistry, 37 (12). pp. 3107-3110. ISSN 0020-1669. doi:10.1021/ic970598k.

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The single-crystal polarized absorption and circular dichroism spectra of the nitridomanganese(V) complexes (salen)Mn⋮N (1), (1S,2S-(−)-saldpen)Mn⋮N (2), and (1R,2R-(+)-saldpen)Mn⋮N (3) have been measured [salen = N,N‘-ethylenebis(salicylideneaminato) dianion, 1S,2S-(−)-saldpen = N,N‘-(1S,2S-(−)-diphenyl)ethylenebis(salicylideneaminato) dianion, and 1R,2R-(+)-saldpen = N,N‘-(1R,2R-(+)-diphenyl)ethylenebis(salicylideneaminato) dianion]. As revealed by X-ray crystal structure analyses, these molecules have a distorted square-pyramidal geometry with a short Mn⋮N bond distance (1.52(3) Å for 2). The Cs compounds have a low-spin^ 1A‘[a‘(x^2 − y^2)]^2 ground state. The lowest absorption system (∼600 nm) consists of two components that are separated by approximately 4000 cm^(-1); these are assigned to ^1A‘ → ^1A‘[a‘(x^2 − y^2)a‘(yz)] (14 900 cm^(-1)) and ^1A‘ → ^1A‘‘[a‘(x^2 − y^2)a‘‘(xz)] (18 900 cm^(-1)) transitions.

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Gray, Harry B.0000-0002-7937-7876
Additional Information:© 1998 American Chemical Society. Received May 19, 1997. We thank J. Du Bois, L. Henling, J. Hong, G. Rossman, and T. Takeuchi for expert technical assistance as well as several helpful discussions. C.J.C. thanks the A. A. Noyes Foundation for a Caltech SURF award. D.W.L. acknowledges the Parsons Foundation for a fellowship. This work was supported by the National Science Foundation.
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Arthur A. Noyes FoundationUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Issue or Number:12
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Official Citation:Electronic Structures of Nitridomanganese(V) Complexes Christopher J. Chang, William B. Connick, Donald W. Low, Michael W. Day, and Harry B. Gray Inorganic Chemistry 1998 37 (12), 3107-3110 DOI: 10.1021/ic970598k
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86659
Deposited By: George Porter
Deposited On:29 May 2018 18:11
Last Modified:15 Nov 2021 20:40

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