Novel organotin-functionalized, polymeric transition metal cyanides from Me3Sn- to Me2Sn(CH2)(3)SnMe2 spacers

The two new compounds [{Me2Sn(CH2)(3)SnMe2}(1.5)Co(CN)(6)], 1, and [{Me2Sn(CH2)(3)SnMe2}(2)Mo(CN)(8)], 2, have been prepared and compared with their notional 'parent' systems [(R3Sn)(3)Co(CN)(6)](R = Me, Et, Bu-n) and solvent-free [(Me3Sn)(4)M(CN)(8)] (M = Mo, W) respectively. Results of extensive spectroscopic (i.e. IR/Raman as well as multinuclear CP MAS NMR) studies and of X-ray powder diffractometry suggest that the crystal structures of 1 and 2 involve three-dimensional networks notably different from those of their 'parent' systems. The probably regular, pairwise linkage of two CNSnMe2CH2 ligand fragments by a third CH2 group even appears to 'improve' the local symmetry of the respective {M(CN)(k)} building block (k = 6 or 8) and simplifies the corresponding asymmetric units. (C) 1997 Elsevier Science S.A.