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Toward the Synthesis of Indenyl Molybdenum Compound [(eta(3)-Ind)(eta(5)-Cp)Mo(CO)(2)]: Modified Compounds and Structure of a Previously Unrecognized Intermediate
Year: 2013
Type of publication: článek v odborném periodiku
Name of source: Organometallics
Publisher name: American Chemical Society
Place: Washington
Page from-to: 3502-3511
Titles:
Language Name Abstract Keywords
cze Příprava indenylových sloučenun molybdenu [(eta(3)-Ind)(eta(5)-Cp)Mo(CO)(2)]: Modifikované sloučeniny a struktura meziproduktu. Mechanismus přípravy [(eta(3)-Ind')(eta(5)-Cp)Mo(CO)(2)] byl studován na metyl-substituovaných derivátech (Ind' = 2-MeC9H6; 4,7-Me2C9H5). Bylo pozorováno, že první krok zahrnující reakci s HCl poskytuje dimerní chloridovou částici [{(eta(5)-Ind')Mo(CO)(2)(mu-Cl)}(2)]. Tento výstup se liší of struktury, která byla navrzena v literatuře. Dále bylo na různých příkladech dokázáno, že tyto sloučeniny {(eta(5)-Ind')Mo(CO)(2)(mu-Cl)}(2)] jsou vhodnými výchozími látkami pro [(eta(3)-Ind')(eta(5)-Cp')Mo(CO)(2)]. Variabilita této metody byla prokázána na několika příkladech zahrnujících slabé Cp donory nesoucí elektronově akceptorní skupiny C5H4COOMe, (1,2-MeOCO)(2)C5H3 a 1,2-((BuNHCO)-Bu-t)(2)C5H3], karbaboran (9-Me2S-7,8-nido-C2B9H10) a škorpionáty (Tp, Tp*). organovovová chemie; koordinační chemie; indenyl; cyklopentadienyl; molybden
eng Toward the Synthesis of Indenyl Molybdenum Compound [(eta(3)-Ind)(eta(5)-Cp)Mo(CO)(2)]: Modified Compounds and Structure of a Previously Unrecognized Intermediate The mechanism of synthesis of [(eta(3)-Ind')(eta(5)-Cp)Mo(CO)(2)] was studied on methyl-substituted derivatives (Ind' = 2-MeC9H6; 4,7-Me2C9H5). It was observed that the initial step involving reaction with HCl gives dimeric chloride species [{(eta(5)-Ind')Mo(CO)(2)(mu-Cl)}(2)]. This outcome differs from the structure suggested in the literature. Furthermore, it was demonstrated by various examples that compounds of the formula [{(eta(5)-Ind')Mo(CO)(2)(mu-Cl)}(2)] are convenient starting materials giving [(eta(3)-Ind')(eta(5)-Cp')Mo(CO)(2)] through the reaction with appropriate cyclopentadienides. The variability of this method was demonstrated on several examples including weakly donating Cp ligands bearing strong electron-withdrawing functional groups [C5H4COOMe, (1,2-MeOCO)(2)C5H3, and 1,2-((BuNHCO)-Bu-t)(2)C5H3] as well as Cp ligands bearing a pendant amine arm (C5H4CH2CH2NMe2). Similar eta(3)-indenyl complexes are formed when using other univalent six-electron ligands such as carbaborane (9-Me2S-7,8-nido-C2B9H10) or scorpionate (Tp, Tp*). The attempts to synthesize [(eta(3)-Ind)(eta(5)-Cp)Mo(CO)(2)] from [(eta(3)-C3H5)(eta(5)-Cp)Mo(CO)(2)] have failed because the initial reaction with HCl does not give the expected [{(eta(5)-Cp)Mo(CO)(2)(mu-Cl)}(2)] but trivial [(eta(5)-Cp)Mo(CO)(3)Cl]. organometallic chemistry; coordination chemistry; indenyl; cyclopentadienyl; molybdenum

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