Influence of ligand polarizability on the reversible binding of O2 by trans-[Rh(X)(XNC)(PPh3)2] (X = Cl, Br, SC6F5, C2Ph; XNC = xylyl isocyanide). Structures and a kinetic study.
作者： Laurence Carlton , Lebohang V. Mokoena , Manuel A. Fernandes
DOI: 10.1021/IC800478G
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摘要: The complexes trans-[Rh(X)(XNC)(PPh 3) 2] (X = Cl, 1; Br, 2; SC 6F 5, 3; C 2Ph, 4; XNC xylyl isocyanide) combine reversibly with molecular oxygen to give [Rh(X)(O 2)(XNC)(PPh of which [Rh(SC 5)(O ( 7) and [Rh(C 2Ph)(O 8) are sufficiently stable be isolated in crystalline form. Complexes 2, 3, 4, 7 have been structurally characterized. Kinetic data for the dissociation O 2 from dioxygen adducts 1- 4 were obtained using (31)P NMR monitor changes concentration 2Ph) resulting bubbling argon through respective warmed solutions (solvent chlorobenzene). From recorded at temperatures range 30-70 degrees C, activation parameters as follows: Delta H (++) (kJ mol (-1)): 31.7 +/- 1.6 Cl), 52.1 4.3 Br), 66.0 5.8 5), 101.3 1.8 2Ph); S (J K (-1) -170.3 5.0 -120 13.6 -89 18.2 -6.4 5.4 2Ph). values closely correlated (R (2) 0.9997), consistent a common pathway along rate-determining step occurs different position each X. Relative magnitudes interpreted terms differing polarizabilities ligands
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