Crystal structure, optical, magnetic, and photochemical properties of the complex pentakis(dimethyl sulfoxide) nitrosylchromium(2+) hexafluorophosphate

Anders Rørbæk Døssing; Anders Kadziola; Johannes Wied Dethlefsen

Crystal structure, optical, magnetic, and photochemical properties of the complex pentakis(dimethyl sulfoxide) nitrosylchromium(2+) hexafluorophosphate

Anders Rørbæk Døssing, Anders Kadziola, Johannes Wied Dethlefsen

Kemisk Institut

6 Citationer (Scopus)

Abstract

The nitrosyl complex [Cr(dmso)₅(NO)](PF₆)₂ (1) (dmso = dimethyl sulfoxide) has been prepared by the solvolysis of [Cr(NCCH₃)₅(NO)](PF₆)₂ in neat dmso. The compound 1 crystallizes in orthorhombic space group Pna2₁ with a = 11.3370(15), b = 24.0790(5), and c = 11.007(3) Å at 122 K with an almost linear Cr-N-O angle (176.45(13)°). The optical absorption spectrum of 1 in dmso shows maxima at 734, 567, 450, 413, and 337 nm. Continuous photolysis of 1 with l = 365 - 580 nm light in dmso solution results in a release of NO with quantum yield, F, in the range 0.034 - 0.108 mol×Einstein^-1. Irradiation of a deoxygenated CH₃CN solution of [Cr(NCCH₃)₅(NO)](PF₆)₂ in the presence of excess of [Fe(S₂CNEt₂)₂] results in a transfer of NO to the iron centre as shown from the characteristic EPR spectrum of [Fe(S₂CNEt₂)₂(NO)] with A_iso(¹⁴N) = 12.2´10^-4 cm^-1. The EPR parameters of 1 were determined: g_iso, g_¦ and g_-: 1.96725, 1.91881(4) and 1.992763(2); A_iso(⁵³Cr), A_¦(⁵³Cr) and A_-(⁵³Cr): 22.8´10^-4, 39´10^-4 and 15.8´10^-4cm^-1; A_iso(¹⁴N), A_¦(¹⁴N) and A_-(¹⁴N): 5.9´10^-4, 2´10^-4 and 7.540(4)´10^-4 cm^-1. The pseudo-first-order rate constant, k, for the substitution of the dmso ligands in 1 with dmso has been found by ¹H NMR in dmso-d₆ solution in the temperature range 293 - 308 K to be k = (8.95 ± 0.09) ´10^-4 s^-1 (t_½ = 12.9 ± 0.1 min) at 298 K with DH^‡ = 100(2) kJ×mol^-1 and DS^‡ = 32(5) J×mol^-1×K^-1.

Udgivelsesdato: April

Originalsprog	Engelsk
Tidsskrift	Inorganica Chimica Acta
Vol/bind	362
Udgave nummer	5
Sider (fra-til)	1585-1590
Antal sider	6
ISSN	0020-1693
Status	Udgivet - 2009

Citationsformater

Crystal structure, optical, magnetic, and photochemical properties of the complex pentakis(dimethyl sulfoxide) nitrosylchromium(2+) hexafluorophosphate. / Døssing, Anders Rørbæk ; Kadziola, Anders; Dethlefsen, Johannes Wied.

I: Inorganica Chimica Acta, Bind 362, Nr. 5, 2009, s. 1585-1590.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

@article{e29c79c0e8af11deba73000ea68e967b,

title = "Crystal structure, optical, magnetic, and photochemical properties of the complex pentakis(dimethyl sulfoxide) nitrosylchromium(2+) hexafluorophosphate",

abstract = " The nitrosyl complex [Cr(dmso)5(NO)](PF6)2 (1) (dmso = dimethyl sulfoxide) has been prepared by the solvolysis of [Cr(NCCH3)5(NO)](PF6)2 in neat dmso. The compound 1 crystallizes in orthorhombic space group Pna21 with a = 11.3370(15), b = 24.0790(5), and c = 11.007(3) {\AA} at 122 K with an almost linear Cr-N-O angle (176.45(13)°). The optical absorption spectrum of 1 in dmso shows maxima at 734, 567, 450, 413, and 337 nm. Continuous photolysis of 1 with l = 365 - 580 nm light in dmso solution results in a release of NO with quantum yield, F, in the range 0.034 - 0.108 mol×Einstein-1. Irradiation of a deoxygenated CH3CN solution of [Cr(NCCH3)5(NO)](PF6)2 in the presence of excess of [Fe(S2CNEt2)2] results in a transfer of NO to the iron centre as shown from the characteristic EPR spectrum of [Fe(S2CNEt2)2(NO)] with Aiso(14N) = 12.2´10-4 cm-1. The EPR parameters of 1 were determined: giso, g¦ and g-: 1.96725, 1.91881(4) and 1.992763(2); Aiso(53Cr), A¦(53Cr) and A-(53Cr): 22.8´10-4, 39´10-4 and 15.8´10-4cm-1; Aiso(14N), A¦(14N) and A-(14N): 5.9´10-4, 2´10-4 and 7.540(4)´10-4 cm-1. The pseudo-first-order rate constant, k, for the substitution of the dmso ligands in 1 with dmso has been found by 1H NMR in dmso-d6 solution in the temperature range 293 - 308 K to be k = (8.95 ± 0.09) ´10-4 s-1 (t½ = 12.9 ± 0.1 min) at 298 K with DH‡ = 100(2) kJ×mol-1 and DS‡ = 32(5) J×mol-1×K-1. Udgivelsesdato: April",

author = "D{\o}ssing, {Anders R{\o}rb{\ae}k} and Anders Kadziola and Dethlefsen, {Johannes Wied}",

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language = "English",

volume = "362",

pages = "1585--1590",

journal = "Inorganica Chimica Acta",

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TY - JOUR

T1 - Crystal structure, optical, magnetic, and photochemical properties of the complex pentakis(dimethyl sulfoxide) nitrosylchromium(2+) hexafluorophosphate

AU - Døssing, Anders Rørbæk

AU - Kadziola, Anders

AU - Dethlefsen, Johannes Wied

N1 - Paper id:: doi:10.1016/j.ica.2008.08.001

PY - 2009

Y1 - 2009

N2 - The nitrosyl complex [Cr(dmso)5(NO)](PF6)2 (1) (dmso = dimethyl sulfoxide) has been prepared by the solvolysis of [Cr(NCCH3)5(NO)](PF6)2 in neat dmso. The compound 1 crystallizes in orthorhombic space group Pna21 with a = 11.3370(15), b = 24.0790(5), and c = 11.007(3) Å at 122 K with an almost linear Cr-N-O angle (176.45(13)°). The optical absorption spectrum of 1 in dmso shows maxima at 734, 567, 450, 413, and 337 nm. Continuous photolysis of 1 with l = 365 - 580 nm light in dmso solution results in a release of NO with quantum yield, F, in the range 0.034 - 0.108 mol×Einstein-1. Irradiation of a deoxygenated CH3CN solution of [Cr(NCCH3)5(NO)](PF6)2 in the presence of excess of [Fe(S2CNEt2)2] results in a transfer of NO to the iron centre as shown from the characteristic EPR spectrum of [Fe(S2CNEt2)2(NO)] with Aiso(14N) = 12.2´10-4 cm-1. The EPR parameters of 1 were determined: giso, g¦ and g-: 1.96725, 1.91881(4) and 1.992763(2); Aiso(53Cr), A¦(53Cr) and A-(53Cr): 22.8´10-4, 39´10-4 and 15.8´10-4cm-1; Aiso(14N), A¦(14N) and A-(14N): 5.9´10-4, 2´10-4 and 7.540(4)´10-4 cm-1. The pseudo-first-order rate constant, k, for the substitution of the dmso ligands in 1 with dmso has been found by 1H NMR in dmso-d6 solution in the temperature range 293 - 308 K to be k = (8.95 ± 0.09) ´10-4 s-1 (t½ = 12.9 ± 0.1 min) at 298 K with DH‡ = 100(2) kJ×mol-1 and DS‡ = 32(5) J×mol-1×K-1. Udgivelsesdato: April

AB - The nitrosyl complex [Cr(dmso)5(NO)](PF6)2 (1) (dmso = dimethyl sulfoxide) has been prepared by the solvolysis of [Cr(NCCH3)5(NO)](PF6)2 in neat dmso. The compound 1 crystallizes in orthorhombic space group Pna21 with a = 11.3370(15), b = 24.0790(5), and c = 11.007(3) Å at 122 K with an almost linear Cr-N-O angle (176.45(13)°). The optical absorption spectrum of 1 in dmso shows maxima at 734, 567, 450, 413, and 337 nm. Continuous photolysis of 1 with l = 365 - 580 nm light in dmso solution results in a release of NO with quantum yield, F, in the range 0.034 - 0.108 mol×Einstein-1. Irradiation of a deoxygenated CH3CN solution of [Cr(NCCH3)5(NO)](PF6)2 in the presence of excess of [Fe(S2CNEt2)2] results in a transfer of NO to the iron centre as shown from the characteristic EPR spectrum of [Fe(S2CNEt2)2(NO)] with Aiso(14N) = 12.2´10-4 cm-1. The EPR parameters of 1 were determined: giso, g¦ and g-: 1.96725, 1.91881(4) and 1.992763(2); Aiso(53Cr), A¦(53Cr) and A-(53Cr): 22.8´10-4, 39´10-4 and 15.8´10-4cm-1; Aiso(14N), A¦(14N) and A-(14N): 5.9´10-4, 2´10-4 and 7.540(4)´10-4 cm-1. The pseudo-first-order rate constant, k, for the substitution of the dmso ligands in 1 with dmso has been found by 1H NMR in dmso-d6 solution in the temperature range 293 - 308 K to be k = (8.95 ± 0.09) ´10-4 s-1 (t½ = 12.9 ± 0.1 min) at 298 K with DH‡ = 100(2) kJ×mol-1 and DS‡ = 32(5) J×mol-1×K-1. Udgivelsesdato: April

M3 - Journal article

SN - 0020-1693

VL - 362

SP - 1585

EP - 1590

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 5

ER -