Darstellung, Schwingungsspektren und Normalkoordinatenanalyse von bindungsisomeren Halogenoselenocyanatorhenaten(IV) sowie Kristallstrukturen von mer-(Ph4P)2[ReCl3(NCSe)2 cis (SeCN)] und mer-(n-Bu4N)2[ReCl3I(NCSe)2 cis] / Synthesis, Vibrational Spectra and Normal Coordinate Analysis of Linkage Isomeric Halogenoselenocyanatorhenates(IV) and Crystal Structures of mer-(Ph4P)2[ReCl3(NCSe)2 cis (SeCN)] and mer-(n-Bu4N)2[ReCl3I(NCSe)2 cis

Abstract

By treatment of fac-[ReCl3I3]2- with (SeCN)2 indichloromethane fac-[ReCl3(NCSe)3]2- (1), mer-[ReCl3(NCSe)2 cis (SeCN)]2- (2) and mer-[ReCl3I(NCSe)2 cis]2- (3) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of mer-(Ph-P)2[ReCl3(NCSe)2 cis(SeCN)] (triclinic, space group Pl̅, a = 16.099(1), b = 16.729(3), c =21.026(2) Å, α = 70.194(10), ß = 73.958(10), γ = 83.929(10)°, Z = 4) and mer-(n-Bu4N)2[ReCl3|(NCSe)2 cis] (monoclinic, space group P21/c, a = 11.838(1), b = 12.796(2), c = 30.767(2) Å, ß = 97.419(6)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.79 (1), 1.71 (2), 1.71 (3) and fd(ReSe) = 1.15 (2) mdyn/Å.