Metal Complexes of Functional Isocyanides, XXIII[1]. ‐ N‐Isocyanodialkylamine Complexes of Boron, Rhodium, Palladium, Platinum, and Copper
The N‐isocyanodialkylamines CNNEt2, CNNiPr2, and CNNCH(Me)(CH2)3CHMe (1a–c) react with triphenylboron, various transition metal halides, and mono‐ and dinuclear chloro complexes by addition, substitution, bridge cleavage and reduction to give the complexes Ph3BCNNR2 (2b, c), [MX2(CNNR2)2] (M = Pd, Pt; X = Cl, Br, I) (3–7), [M(Cl)‐(CNNR2)(PPh3)2]BF4 (8, 9), cis‐ and trans‐[PtCl2(CNNR2)‐(PR′3)] (R′ = Et, Ph) (10–12), [Rh(CNNR2)4]Cll (15b, c) and [Cu(CNNR2)4]ClO4 (16b, c). The complexes [PdX2(CNNR2)(PPh3)] (X = Cl, Br) (13c, 14c) have been obtained by substitution of an N‐isocyanide ligand in 3c and 4c, respectively, with PPh3. The structural assignments are made on the basis of IR, NMR (1H, 13C, 31P, 15N) and mass spectrometry as well as of an X‐ray structure analysis of [PdI2(CNNiPr2)2] (5b).