Synthesis and Reactivity of Bis(ethene) Rhodium(I) and Iridium(I) Carboxylato Complexes

Autor: Sybo Poelsma, Dietmar Barth, Helmut Werner, Michael Schneider, Bettina Windmüller
Rok vydání: 1996
Předmět:
Zdroj: Chemische Berichte. 129:647-652
ISSN: 0009-2940
DOI: 10.1002/cber.19961290609
Popis: [Rh(μ-O2CCH3)(C2H4)2]2 (3) and analogous carboxylatobis-(olefin)rhodium(I) complexes [Rh(μ-O2CR)(olefin)2]2 (4–6) were almost quantitatively prepared under heterogeneous conditions from [RhCl(C8H14)2]2 (1) or [RhCl(C2H4)2]2 (2) and CH3CO2Na · 3 H2O or RCO2H/NaOH, respectively. The X-ray crystal structure analysis of 3 confirmed the bridging position of the acetato ligands. The synthesis of [Ir(μ-O2CCH3)(C2H4)2]2 (10) was carried out similarly by using [IrCl(C2H4)2]2 (8) and CH3CO2Na · 3 H2O as starting materials. The monoethene complex trans-[Ir(η1-O2CCH3)(C2H4)-(PiPr3)2] (11) was obtained from 10 and PiPr3; it reacted with H2 and HCCPh by oxidative addition to give [IrH2(η2-O2CCH3)(PiPr3)2] (12) and [IrH(CCPh)(η2-O2CCH3)(PiPr3)2] (14), respectively. Compound 12 was also prepared from [IrH2Cl(PiPr3)2] (13) and CH3CO2Na · 3 H2O. The new bis-(ethene)complexes 3, [Rh(μ-O2CC6H5)(C2H4)2]2 (6) and 10 are catalytically less active than 2 in the reaction of C2H4 and Ph2CN2 and gave as C–C coupling product not only 1,1-diphenylpropene (16) but also mixtures of 16 and 1,1-diphenylcyclopropane (17) in different ratios.
Databáze: OpenAIRE