A Dinuclear Phosphidoplatinum( II ) Fragment as a Building Block for Tri‐, Tetra‐, Hexa‐, and Octanuclear Complexes

The dinuclear complex [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(NCCH 3 ) 2 ] ( 1 ) is described and fully characterised. Complex 1 reacts with 2,2′‐bipyrimidine and cis ‐[M(C 6 F 5 ) 2 (THF) 2 ] to form the di‐, tri‐ and tetranuclear complexes 2 , 3 and 4 , respectively, depending on the ratio of reagents and the type of metal (M = Pt, Pd). Complex 1 reacts with KCN to form the anionic dinuclear complex [PPh 3 (CH 3 )] 2 [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(CN) 2 ] ( 6 ). Complex 6 acts as a metalloligand towards cis ‐[M(C 6 F 5 ) 2 (THF) 2 ] or 1 to yield the corresponding hexanuclear or octanuclear complexes 7 , 8 and 9 . The structure of [PPh 3 (CH 3 )] 4 [{(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(μ‐CN) 2 Pd(C 6 F 5 ) 2 } 2 ] ( 8 ) has been established by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)