Fluxionality and Phosphane Arm-off Reactions of Octahedral Ruthenium(II) Complexes with the Tripodal Polyphosphane MeC(CH2PPh2)3

Effects of the Heterocycle and Its Substituents on Structure and Fluxionality in Rhodium(I) and Iridium(I) Complexes with the Hindered Thiolates 6-tert-Butylpyridine-2-thiolate and 1-Alkyl-4-tert-butylimidazole-2-thiolate (alkyl = methyl andtert-butyl)

“…In fact, from literature structures of 1-methyl-imidazole-2-thiolate complexes, coordination through only the sulfur atom appears to be rare, whether in mononuclear complexes or in dinuclear species as bridging [μ-(1:2κ 2 S)] ligands . Instead, the more usual coordination modes of this ligand are μ-(1κS,2κN), μ-(1κN,1:2κS), and (κ 2 S,N) . In general, three factors may explain the higher propensity of the imidazole derivatives to act as bidentate ligands.…”

“…Coordination of pyridine-2-thiolate (PyS) to Rh(I) and Ir(I) species as in M 2 (PyS) 2 L 1 L 2 , where L 1 and L 2 are CO, alkenes, or CO and phosphine, has established that doubly bridged species of types C and E could be formed and may interconvert in solution . The closely related species 1-alkylimidazole-2-thiolate has to our knowledge not been examined on Rh(I) or Ir(I), although it has shown a variety of coordination modes in other systems. − In the work reported here, we chose to increase steric hindrance at the basic heterocyclic nitrogen by using derivatives with an adjacent tert -butyl group. In addition, studying the effect of the steric environment of the thiolate sulfur was accomplished in the imidazole series by making 1-methyl and 1- tert -butyl derivatives.…”

Ruthenium η4-Trimethylenemethane Complexes Containing Tripodal Phosphanomethylamine Ligands

“…Tripodal phosphine ligands have attracted interest as ancillary ligands for late transition metals ever since the introduction of Triphos . Complexes containing this ligand, , its P-substituted derivatives, and other tripodal phosphines such as N-Triphos, Sul-phos, Sn- and Si-Triphos, Siliphos, MT-Siliphos, and N(CH 2 CH 2 PPh 2 ) 3 , as well as several tris-phospholane ligands, − have been synthesized and employed in catalytic reactions.…”

Chlorocarbonyl ruthenium(II) complexes of tripodal triphos {MeC(CH2PPh2)3}: Synthesis, characterization and catalytic applications in transfer hydrogenation of carbonyl compounds

“…Tridentate tripodal phosphines are recognized as one of the most important classes of ligands having widespread applications in coordination chemistry [1][2][3][4][5][6][7][8][9][10]. Such ligands provide an important advantage over monodentate phosphines with respect to greater control of the coordination number, stoichiometry and stereochemistry of their complexes [11].…”