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• W1964047650 startingPage "2638" @default.
• W1964047650 abstract "Protonation of the methylene-bridged complex [RhOs(CO)3(μ-CH2)(μ-CO)(dppm)2][CF3SO3] with triflic acid at −80 °C yields the methyl complex [RhOs(CO)4(μ-CH3)(dppm)2][CF3SO3]2 (1) in which the methyl group is primarily bound to Os while involved in an agostic interaction with Rh. Warming this species to −20 °C results in methyl migration to a terminal site on Rh, yielding [RhOs(CH3)(CO)2(μ-CO)2(dppm)2][CF3SO3]2 (2), and subsequent warming to ambient temperature results in migratory insertion to yield the acetyl-bridged [RhOs(CF3SO3)(CO)2(μ-C(CH3)O)(μ-CO)(dppm)2][CF3SO3] (3). Replacement of the coordinated triflate anion in 3 by CO and PMe3 occurs at low temperature to give [RhOs(L)(CO)2(μ-C(CH3)O)(μ-CO)(dppm)2][CF3SO3]2 (L = CO (4), PMe3 (5a)). Warming the PMe3 adduct results in transformation of the acetyl group, which is C-bound to Rh in 5a, to a group that is C-bound to Os in 5b. One carbonyl in 3 is labile and is readily lost, yielding [RhOs(CF3SO3)(CO)2(μ-C(CH3)O)(dppm)2][CF3SO3] (6). Attempts to obtain the above methyl or acetyl species by reaction of the hydride-bridged species [RhOs(X)(CO)3(μ-H)(μ-CO)(dppm)2][X] (X = CF3SO3 (7a), BF4 (7b)) with diazomethane were unsuccessful." @default.
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• W1964047650 date "2003-05-23" @default.
• W1964047650 modified "2023-09-25" @default.
• W1964047650 title "Methylene-to-Acetyl Conversion in Heterobinuclear Rh/Os Complexes: Models for Oxygenate Formation by Bimetallic Fischer−Tropsch Catalysts" @default.
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• W1964047650 doi "https://doi.org/10.1021/om030282m" @default.
• W1964047650 hasPublicationYear "2003" @default.
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