Abstract
Complexation of Pd 2+ by CN − in liquid ammonia has been studied by means of IR and Raman spectra of the solutions. Stepwise complexation occurs up to the squareplanar 4 : 1 species. In the 2 : 1 step trans-Pd(CN) 2 is initially formed at subambient temperatures but slowly equilibrates ( t 1/2 = 6 h) at 293 K into a mixture containing both the cis and the trans isomers. The 2 : 1 and 4 : 1 complexes appear to be thermodynamically very stable. All the 11 CN stretching modes of vibration of [(NH 3) 3Pd(CN)] +, cis- and trans-[(NH 3) 2Pd(CN) 2], [(NH 3)Pd(CN) 3] − and [Pd(CN) 4] − have been observed and assigned. There is no spectroscopic evidence for multinuclear complexation involving bridging CN − groups.
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