METAL-COMPLEXES OF FUNCTIONAL ISOCYANIDES .24. REACTIONS OF N-ISOCYANODIALKYLAMINE COMPLEXES WITH SECONDARY-AMINES

Reactions of pentacarbonyl(N-isocyanodialkylamine) group 6-metal complexes [M(CO)5CNNR2][M = Cr, W; R = Et, iPr; 2R = -{MeCH(CH2)3CHMe}-] with secondary amines proceed with cleavage of the N-N bond and C-->N migration of the metal to give the corresponding N-cyanamide complexes [M(CO)5NCNR'2] (1a-2g) [R'= Me, Et, nPr, nBu; 2R' = -(CH2)4-, -(CH2)5-, -(CH2)2O(CH2)2-]. However, when diiodobis(N-isocyanodialkylamine)platinum(II) was allowed to react with an excess of the amine amine(guanidine)platinum(II) complexes [PtI2(HNR'2){HN=C(NR2'2)2}](3a-c) [R' = Et; 2R' = -(CH2)5-, -(CH2)2O(CH2)2-] were obtained. Structural assignments are made on the basis of IR, NMR (H-1, C-13) , and mass spectroscopy as well as of an X-ray structure analysis of trans-[PtI2(HNEt2){HN=C(NEt2)2}] (3a).