ISSN:
0009-2940
Keywords:
Rh coordination complex
;
Organometallic aqua ions
;
Olefin complex
;
Olefin exchange
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Dehalogenation of halide precursors [(olefin)RhCl]2 [olefin = ethylene, 1,5-cyclooctadiene (COD], norbornadiene (NBD), 2,3-dimethylbutadiene (DMB)] in water gave the respective cis-diolefin aqua ions, characterized by NMR spectroscopy in solution. Attempted isolation of the tosylate salt [(COD)Rh-(H2O)2]OTs yielded crystals of (COD)Rh(H2O)(η1-OTs) characterized by X-ray structural analysis. [(NBD]Rh(H2O)2]SbF6 in the presence of adventitious toluene decomposed into [(NBD])Rh(η6-toluene)]SbF6 and [(NBD]2Rh]SbF6, both complexes were isolated and structurally characterized. Ethylene exchange in [(C2H4)2Rh(H2O)2]+ is fast with k2 of the order of 104-105 s-1 · M-1. The rate constant for water exchange in [CODRh(H2O)2]+ is estimated as 104 s-1 (ΔDLG≠173 ≍ 25 kJ/mol) at 173 K.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951280910
