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

Abstract

The dinuclear complex [(C6F5)2Pt(μ‐PPh2)2Pt(NCCH3)2] (1) is described and fully characterised. Complex 1 reacts with 2,2′‐bipyrimidine and cis‐[M(C6F5)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 [PPh3(CH3)]2[(C6F5)2Pt(μ‐PPh2)2Pt(CN)2] (6). Complex 6 acts as a metalloligand towards cis‐[M(C6F5)2(THF)2] or 1 to yield the corresponding hexanuclear or octanuclear complexes 7, 8 and 9. The structure of [PPh3(CH3)]4[{(C6F5)2Pt(μ‐PPh2)2Pt(μ‐CN)2Pd(C6F5)2}2] (8) has been established by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Discrete Molecular Squares {[(en)M(CN)]4}4+ Derived from [(en)M(CN)2] (M = PtII, PdII)

“…Although for the tetrameric [Me 2 Au(CN)] 4 (Me = methyl) a type‐ I isomer has been postulated, 1 H NMR spectroscopy suggests the presence of disordered CN – ligands 11. X‐ray crystal structures of cyclic CN‐bridged Pt II compounds are scarce and reveal both disordered12a and ordered CN – bridges 12b,12c. A further potential complication arises from the possibility of equilibria between squares and triangles.…”

An organometallic tetranuclear cluster with phosphine and phosphido ligands in nonclassical bonding modes: X-ray structural characterization

“…Complexes [(C 6 F 5 ) 2 M(lPPh 2 ) 2 M 0 (NCCH 3 ) 2 ] (M = Pt, M 0 = Pd 3; M = M 0 = Pt, 4, Pd 5) were prepared as described in the references [3,59].…”

Bridging and Terminal (Phosphanido)platinum Complexes

“…When 6 is reacted with PtCl 2 , the tetranuclear compound [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(μ‐Cl)] 2 ( 95 ) is obtained, which proved to be a precursor of several phosphanido‐bridged di‐ and polynuclear compounds as well as of the bis(acetonitrile) complex [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(CH 3 CN) 2 ] ( 96 ), which, in turn, gives the bis(cyano) complex [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(CN) 2 ] 2– ( 97 ) by ligand substitution (Scheme ) 76. The organometallic phosphanido‐bridged dinuclear compounds originating from 95 are shown in Scheme .…”

“…Moreover, the controlled‐nuclearity growth of complexes or clusters stabilised by phosphanido bridges paves the way to the assembly of large molecular frameworks with predefined shape. For instance, the cyano complex [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(CN) 2 ] 2– ( 97 ) acts a “metalloligand”, giving the corresponding hexa‐ or octanuclear complexes by reaction with cis ‐[Pt(C 6 F 5 ) 2 (thf) 2 ] or [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(CH 3 CN) 2 ] ( 96 ), respectively 76. Other relevant examples are the hexanuclear complexes 133 and 134 composed of two cyclic triplatinum units connected with 1,4‐phenylene or 1,1′‐ferrocenylene spacers (Scheme ) 113…”