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Published June 15, 1998 | Supplemental Material
Journal Article Open

Electronic Structures of Nitridomanganese(V) Complexes

Abstract

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.

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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