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- W1969969583 abstract "The heat-promoted reaction of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene with cyclomanganated 2-[tricarbonyl(η6-phenyl)chromium]pyridine afforded, upon departure of a molecule of CO, a new stable manganese alkylidene complex in which, according to X-ray diffraction analyses, the heterocyclic ligand is anti-facial with respect to the Cr(CO)3 moiety. Similar heat-promoted reactions of unsymmetrically substituted diazoalkanes such as (Me3Si)(H)CN2, (Ph)(Me)CN2, (Ph)(t-Bu)CN2 and (Ph)(FcCH2CH2)CN2, which are precursors of more electrophilic alkylidenes, with cyclomanganated 2-[tricarbonyl(η6-phenyl)chromium]pyridine derivatives afforded new syn-facial heterobimetallic benzyl complexes. The stereoselectivity of these reactions depends on the steric demand of the substituents at the diazoalkane. A phenyl substituent at the diazoalkane favors the formation of syn-facial heterobimetallic benzyl complexes with the Ph group in the endo position. Combining this “phenyl directing effect” to the steric effect operated by a bulky group at the phenyldiazoalkane, like noticed with (Ph)(t-Bu)CN2, led to total stereoselectivity. This study discloses four new X-ray structures of syn-facial Cr,Mn benzyl complexes, which all present the same short Cr-to-Mn distance of ca. 3.04 Å." @default.
- W1969969583 created "2016-06-24" @default.
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- W1969969583 date "2006-02-01" @default.
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- W1969969583 title "Synthesis of syn-facial (Cr,Mn) benzyl complexes by the stereoselective thermolytic coupling of unsymmetric diazomethanes with cyclomanganated (η6-arene)tricarbonylchromium complexes" @default.
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- W1969969583 doi "https://doi.org/10.1016/j.jorganchem.2005.10.029" @default.
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