Chromium carbonyl complexes with aryl mono- and oligogermanes: Ability for haptotropic rearrangementстатья

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Дата последнего поиска статьи во внешних источниках: 11 ноября 2019 г.

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[1] Chromium carbonyl complexes with aryl mono- and oligogermanes: Ability for haptotropic rearrangement / K. V. Zaitsev, I. P. Gloriozov, Y. F. Oprunenko et al. // Journal of Organometallic Chemistry. — 2019. — Vol. 897. — P. 217–227. The intra- and intermolecular inter-ring η6 # η6 -haptotropic rearrangements (IRHR), occurring by involving interactions to Ge atoms in arylgermanes, were investigated theoretically and experimentally. The new methods for the synthesis of non-symmetrical polyaromatic Ge compounds were elaborated. Digermane Ph3GeGeMe2Cl (2) was obtained from Ph3GeGeMe2NMe2 (1) under action of Me3SiCl. Aryl digermane Ph3GeGeMe2(η6 -C6H5)Cr(CO)3 (4) was obtained after lithiation of (η6 -C6H6)Cr(CO)3 (3) with subsequent interaction with 2. It was established that thermally induced intramolecular IRHR in 4 is not observed experimentally; at similar reaction conditions in the presence of tetralin C10H12 (7) the bimolecular intermolecular IRHR occurs giving (η6 -C10H12)Cr(CO)3 (8). DFT analysis of the intramolecular IRHRs for model germane (p-Tol)2Ge(H)(η6 -Tol-p)Cr(CO)3 (MC1) and digermane Ph3GeGeH2(η6 -C6H5) Cr(CO)3 (MC2) indicates a plausible effect of 3c-2e (agostic) Ge-H...Cr interaction on success of such rearrangement. The theoretical activation barrier is determined to be in the range of 35-37 kcal/mol. The model compound (η6 -C6H3(GeHPh2)Me2-p)Cr(CO)3 (12) was obtained from (η6 -C6H4Me2-p)Cr(CO)3 (11). The decomposition of 12 was observed under conditions of thermally induced IRHR. Molecular structures of 8, 11 and 12 in a crystal were investigated by XRD. [ DOI ]

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