Electronic Structures of Nitridomanganese(V) Complexes

Christopher J. Chang; William B. Connick; Donald W. Low; Michael W. Day; Harry B. Gray

doi:10.1021/ic970598k

Electronic Structures of Nitridomanganese(V) Complexes

Christopher J. Chang, William B. Connick, Donald W. Low, Michael W. Day, Harry B. Gray

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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 C_s compounds have a low-spin ¹A′[a′(x² y²)]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′(x² - y²)a′(yz)] (14 900 cm^-1) and ¹A′ → ¹A″[a′(x² - y²)a″(xz)] (18 900 cm^-11) transitions.

Original language	English (US)
Pages (from-to)	3107-3110
Number of pages	4
Journal	Inorganic Chemistry
Volume	37
Issue number	12
DOIs	https://doi.org/10.1021/ic970598k
State	Published - Jun 1 1998
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic970598k

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@article{b8ce673859084642976649de828baa58,

title = "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) {\AA} for 2). The Cs compounds have a low-spin 1A′[a′(x2 y2)]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′(x2 - y2)a′(yz)] (14 900 cm-1) and 1A′ → 1A″[a′(x2 - y2)a″(xz)] (18 900 cm-11) transitions.",

author = "Chang, {Christopher J.} and Connick, {William B.} and Low, {Donald W.} and Day, {Michael W.} and Gray, {Harry B.}",

year = "1998",

month = jun,

day = "1",

doi = "10.1021/ic970598k",

language = "English (US)",

volume = "37",

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journal = "Inorganic Chemistry",

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TY - JOUR

T1 - Electronic Structures of Nitridomanganese(V) Complexes

AU - Chang, Christopher J.

AU - Connick, William B.

AU - Low, Donald W.

AU - Day, Michael W.

AU - Gray, Harry B.

PY - 1998/6/1

Y1 - 1998/6/1

N2 - 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′(x2 y2)]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′(x2 - y2)a′(yz)] (14 900 cm-1) and 1A′ → 1A″[a′(x2 - y2)a″(xz)] (18 900 cm-11) transitions.

AB - 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′(x2 y2)]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′(x2 - y2)a′(yz)] (14 900 cm-1) and 1A′ → 1A″[a′(x2 - y2)a″(xz)] (18 900 cm-11) transitions.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

Electronic Structures of Nitridomanganese(V) Complexes

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