Molecular and crystal structure of tris(acetonitrile)nitrosylbis(triphenylphosphine)rhodium(III) dication as its hexafluorophosphate salt

Abstract

Crystals of [Rh(NCMe)₃(NO)(PPh₃)₂][PF₆]₂ are monoclinic, space group P2₁/n, with a= 14.053(8), b= 27.512(15), c= 11.914(8)Å, β= 97.29(5)°, and Z= 4. The structure has been elucidated by the analysis of 8 502 observed intensities recorded at ca. 215 K on a four-circle diffractometer, and refined by least squares to R 0.075. In the cation the metal is octahedrally bound to trans-phosphorus atoms (mean Rh–P 2.405 Å) and three acetonitrile ligands [Rh–N 2.030(7). 2.104(7), and 2.308(8)Å] the last lying trans to the nitrosyl function [Rh–NO 2.026(8)Å] which acts as the one-electron donor [NO]^–[Rh–N–O 118.4(6)°]. The two hexafluorophosphate counter ions exhibit differing thermal activity which is correlated to their crystal environments.