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The synthesis of novel heterobimetallic derivatives of general formula [RuClCp(PPh3)-μ-dmoPTA-1κP:2κ2N,N′-M(acac-κ2O,O′)2] (M = Ni (3), Zn (4); dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) is described. The preparations of the ruthenium–cobalt analogue (M = Co (2)) and the starting compound [RuClCp(HdmoPTA-κP)(PPh3)](CF3SO3) have been revised and their yield improved. Similar to 2, the solid state structures of 3and 4show that the dmoPTA-P and the dmoPTA-NCH3atoms are involved in the coordination to the {RuCpCl(PPh3)} and {M(acac)2} moieties, respectively. The size of the diffusing units is almost the same for the three binuclear complexes, indicating that they exhibit similar solution structures. The diamagnetic ruthenium–zinc derivative was fully characterized in solution at 193 K by NMR as two diastereomeric pairs of enantiomers (R-Ru, Δ-Zn; R-Ru, Λ-Zn; S-Ru, Δ-Zn; S-Ru, Λ-Zn). Finally, the electrochemical properties of the complexes have been investigated by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

The reaction of HTIMP3(HTIMP3= tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane) with [RhCl(COD)]2and Rh(acac)(CO)2produces RhHCl(TIMP3) (1H) and Rh(TIMP3)(CO) (2), respectively, both exhibiting tetradentate κC,κ3P-coordination of the TIMP3moiety. The reaction of RhHCl(TIMP3) with nucleophiles (L) in the presence of AgBF4or AgPF6produces different compounds depending on the nature of L. Indeed, cationic Lewis adducts of formula [RhH(L)(TIMP3)]+(2H+-5H+) are obtained when L is CO, CNCH2Ph, pyridine or CH2CHCN. On the other hand, when the incoming nucleophile is CH3COOH the hydride-free complex [Rh(CH3COO)(TIMP3)]+(6+) is obtained. Finally, the reaction of RhHCl(TIMP3) with PhCCPh and CH2CHCOOMe in the presence of AgPF6leads to the insertion products [Rh(PhCCHPh)(TIMP3)]+(7+) and [Rh(CH2CH2COOMe)(TIMP3)]+(8+), respectively. The solid state structure has been determined by single crystal X-ray diffraction in selected cases (1H, 6+). [ABSTRACT FROM AUTHOR]