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

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 optical absorption spectrum of 1 in dmso shows maxima at 734, 567, 450, 413, and 337 nm. Continuous photolysis of 1 with lambda = 365-580 nm light in dmso solution results in a release of NO with quantum yield, Phi, 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)(N-14) = 12.2 x 10 (4) cm (1). The EPR parameters of 1 were determined: g(iso), g(parallel to) and g(perpendicular to) : 1.96725, 1.91881(4) and 1.992763(2); A(iso)(Cr-53), A(parallel to) (Cr-53) and A(perpendicular to)(Cr-53): 22.8 x 10 (4), 39 x 10 (4) and 15.8 x 10 (4) cm (1); A(iso)(N-14), A(parallel to) (N-14) and A(perpendicular to)(N-14): 5.9 x 10 (4), 2 x 10(4) and 7.540(4) x 10 (4) cm (1). (C) 2008 Elsevier B.V. All rights reserved.