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• W2019298646 abstract "The tetradentate dianionic Schiff base ligand Bu4salophenH2 reacts with [RhCl(C2H4)2]2 and NR4OH (R = n-Bu, Et) to produce the complexes RhR(Bu4salophen) (1, R = n-Bu; 2, R = Et), which undergo photolysis (λ > 475 nm) under a hydrogen atmosphere to generate RhH(Bu4salophen) (3) and the corresponding alkanes. In benzene at room temperature, olefins insert into the metal−hydride bond of 3 to produce Rh(CH2CH2R)(Bu4salophen) (2, R = Et; 4, R = Ph; 5, R = CN). In a competition experiment, insertion of styrene is only slightly favored over that of ethylene. For olefinic substrates capable of radical rearrangement (CH2CHR where R = CH2OCH2CHCH2 and c-C3H5), insertion products are formed that do not correspond to radical rearrangements. Specifically, Rh(CH2CH2OCH2CHCH2)(Bu4salophen) (6) is observed as the only product of the reaction of 3 with bis(allyl) ether while Rh(CH2CH2-c-C3H5)(Bu4salophen) (7) is seen as the major product in the reaction with vinylcyclopropane. For the vinylcyclopropane reaction, additional products are also identified by 2D NMR methods as Rh(CH2CH2CHCHCH3)(Bu4salophen) (8) and (Bu4salophen)Rh(μ-CH2CH2CHCHCH2)Rh(Bu4salophen) (9). Both the poor selectivity for styrene versus ethylene insertion and the absence of radical rearranged product with bis(allyl) ether and vinylcyclopropane indicate that, in the reaction of 3 with olefins, an intermediate containing a pure carbon-based radical is not involved." @default.
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• W2019298646 date "1996-03-19" @default.
• W2019298646 modified "2023-10-17" @default.
• W2019298646 title "Reactions of the Schiff Base Rhodium Hydride Complex RhH(Bu₄salophen) with Olefins. Observations and Mechanistic Studies" @default.
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• W2019298646 doi "https://doi.org/10.1021/om950595k" @default.
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