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Synthesis, characterization and reactivity of tribenzylphosphine rhodium and iridium complexes |
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| Authors: | Vanessa R Landaeta Maurizio Peruzzini Verónica Herrera Roberto A Sánchez-Delgado Andrés E Goeta |
| Institution: | a Instituto Venezolano de Investigaciones Científicas (IVIC), Centro de Química, Apartado 21827, Caracas, 1020-A, Venezuela b Istituto di Chimica dei Composti Organometallici (ICCOM - CNR), Area Ricerca CNR Firenze, Via Madonna del Piano 10, 50019 Sesto Fiorentino (FI), Italy c Chemistry Department, Brooklyn College of The City University of New York Brooklyn, NY 11210, USA d University of Durham, Department of Chemistry, Science Site, South Road, Durham DH1 3LE, UK |
| Abstract: | New rhodium and iridium complexes, with the formula MCl(PBz3)(cod)] M = Rh (1), Ir (2)] and M(PBz3)2(cod)]PF6 M = Rh (3), Ir (4)] (cod = 1,5-cyclooctadiene), stabilized by the tribenzylphosphine ligand (PBz3) were synthesized and characterized by elemental analysis and spectroscopic methods. The molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction. The addition of pyridine to a methanol solution of 1or 2, followed by metathetical reaction with NH4PF6, gave the corresponding derivatives M(py)(PBz3)(cod)]PF6 M = Rh (5), Ir (6)]. At room temperature in CHCl3 solution, 4 converted spontaneously to the ortho-metallated complex IrH(PBz3)(cod){η2-P,C-(C6H4CH2)PBz2}]PF6 (7) as a mixture of cis/trans isomers via intramolecular C-H activation of a benzylic phenyl ring. The reaction of 3 or 4 with hydrogen in coordinating solvents gave the dihydrido bis(solvento) derivative M(H)2(S)2(PBz3)2]PF6 (M = Rh, Ir; S = acetone, acetonitrile, THF), that transformed into the corresponding dicarbonyls M(H)2(CO)2(PBz3)2]PF6 by treatment with CO. Analogous cis-dihydrido complexes M(H)2(THF)2(py)(PBz3)2]PF6 (M = Rh, Ir) were observed by reaction of the py derivatives 5 and 6 with H2. |
| Keywords: | Rhodium Iridium Tribenzylphosphine C-H bond activation X-ray crystallography Ortho-metallation |
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