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- W4249423193 abstract "The bulky ligands Lx− (Lx=(2, 6-C6H3X2)NC(Me)CHC(Me)N(2, 6-C6H3X2), X=Cl, Me) can be used to generate fluxional mononuclear arene complexes [LXRh(η4-arene)] (arene=benzene, toluene, m-xylene, mesitylene), which for X=Me disproportionate to fluxional dinuclear complexes [{LMeRh}2(anti-μ-arene)]. For both mononuclear and dinuclear complexes, steric interactions do not stop the fluxionality but govern the preferred orientation of the methyl-substituted arenes, thus allowing indirect determination of the static NMR parameters. For the μ-arene complexes, two distinct types of fluxionality are proposed on the basis of calculations: ring rotation and metal shift. In the solid state, the toluene complex has an η4(1,2,3,4):η4(3,4,5,6)-bridged structure; the NMR analysis indicates that the benzene and m-xylene complexes have similar structures. The mesitylene complex, however, has an unprecedented η3(1,2,3):η3(3,4,5)-bridged structure, which is proposed to correspond to the transition state for arene rotation in the other cases. Steric factors are thought to be responsible for this reversal of stabilities." @default.
- W4249423193 created "2022-05-12" @default.
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- W4249423193 date "2000-08-04" @default.
- W4249423193 modified "2023-09-23" @default.
- W4249423193 title "Steric Control over Arene Coordination to -Diiminate Rhodium(I) Fragments" @default.
- W4249423193 doi "https://doi.org/10.1002/1521-3765(20000804)6:15<2740::aid-chem2740>3.3.co;2-s" @default.
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