ISSN:
0009-2940
Keywords:
Rhodium(I) complexes
;
Carboxylate bridges
;
Iridium(I) complexes
;
Acetato ligands
;
Iridium(III) complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
[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 HC≡CPh by oxidative addition to give [IrH2(η2-O2CCH3)(PiPr3)2] (12) and [IrH(C≡CPh)(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.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961290609
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