Metal Complexes of Functional Isocyanides, XXV. Amino(hydrazino)carbene Complexes

The N ‐isocyanodialkylamine metal complexes [M(CO) 5 CN‐NR 2 ] (M = Cr, W), trans ‐[MI 2 (CNNR 2 ) 2 ] (M = Pd, Pt), trans ‐[Pt(Cl)(CNNR 2 )(PPh 3 ) 2 ]BF 4 , and cis ‐[PtCl 2 (CNNR 2 )(PPh 3 )] [R = Et, i Pr; 2 R = ‐{CHMe(CH 2 ) 3 CHMe}‐] react with primary amines to give the amino(hydrazino)carbene metal complexes [M(CO) 5 (C(NHR′)NHNR 2 }] (R′ = Me, n Pr, Cy) ( 1–9 ), trans ‐[PtI 2 {C(NHMe)NHNR 2 } 2 ] ( 10–12 ) and trans, and the amine adducts cis ‐[PtCl 2 {C(NHMe)NHNC(H)(Me) (CH 2 ) 3 CHMe}(PPh 3 )]H 2 NMe ( 14 ), and trans ‐[PdI 2 {C (NHMe)NHNC(H)(Me)(CH 2 ) 3 CHMe} 2 ]2 H 2 NMe ( 15 ). With secondary amines the amino(hydrazino)carbene metal complexes trans( 18 ) and trans ‐[PtCl{C(NEt 2 )NHNEt 2 } (PPh 3 ) 2 ]BF 4 ( 19 ) Were isolated. The complexes trans ‐[PtI 2 {C(NHCy)NHN i Pr 2 }CNN i Pr 2 ] ( 20 ) and trans ‐[PdI 2 (NH 2 Cy){C(NHCy)NHN i Pr 2 }] ( 21 ) were obtained by reaction of trans ‐[MI 2 (CNN i Pr 2 ) 2 ] (M = Pd, Pt) with cyclohexylamine. The structures were assigned on the basis of IR, NMR‐ ( 1 H, 13 C, 31 P), and mass spectroscopy as well as an X‐ray structural analysis of 21 .