Abstract
The dinuclear complex [{Pd(µ-SPPh2)(C6F5)(PPh3)}2] reacted with the cationic precursors [PdL(Me2CO)2]+[L = 2-(dimethylaminomethyl)phenyl-C1,N, quinolin-8-ylmethyl-C,N or phenylazophenyl-C1,N] and with the neutral precursors [M(C6F5)2(thf)2](M = Pd or Pt, thf = tetrahydrofuran) to give the corresponding cationic homotrinuclear complexes [Pd3(µ3-SPPh2)2(C6F5)2L(PPh3)2]ClO4(L = C6H4CH2NMe2-2 1, NC9H6CH2-8 2 or PhNNC6H43) and the neutral homo- and hetero-trinuclear complexes [Pd2M(µ3-SPPh2)2(C6F5)4(PPh3)2](M = Pd 4 or Pt 5) in which the [SPPh2]– group acts as a triply-bridging ligand. Complexes 1–5 have been characterized by spectroscopic methods (IR; 1H, 19F and 31P-{1H} NMR) and the molecular structure of [Pd3(µ3-SPPh2)2(C6F5)2(C6H4CH2NMe2–2)(PPh3)2]ClO41 has been determined crystallographically. Complex 1·0.8CH2Cl2 crystallizes in the monoclinic system, space group P21/c, a= 14.185(3), b= 21.589(4), c= 27.440(5)A, β= 104.95(3)° and Z= 4. The model refined to final values of R= 0.0702 and R′= 0.0849 for 5989 observed reflections [F > 4.0σ(F)] and 860 parameters. The structure shows that the [Pd(µ-SPPh2)(C6F5)(PPh3)]2 unit behaves as a cyclic bidentate sulfur ligand, co-ordinated to the [Pd(C6H4CH2NMe2-2)]+ group through the two S atoms. The central Pd3(SPPh2)2 cage contains two µ3-SPPh2 ligands linking the three palladium atoms.
Published Version
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