Reactivity Studies of Oxo鈥揗o(IV) Complexes Containing Potential Hydrogen-Bond Acceptor/Donor Phenolate Ligands

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• 作者：Victor Wee Lin Ng ; Michelle K. Taylor ; Charles G. Young
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：March 5, 2012
• 年：2012
• 卷：51
• 期：5
• 页码：3202-3211
• 全文大小：528K
• 年卷期：v.51,no.5(March 5, 2012)
• ISSN：1520-510X

文摘

Reactivity studies of oxo鈥揗o(IV) complexes, Tp^iPrMoO{2-OC₆H₄C(O)R-魏²O,O鈥瞹 (R = Me, Et, OMe, OEt, OPh, NHPh), containing chelated hydrogen-bond donor/acceptor phenolate ligands are reported. Hydrolysis/oxidation of Tp^iPrMoO(2-OC₆H₄CO₂Ph-魏²O,O鈥? in the presence of methanol yields tetranuclear [Tp^iPrMoO(渭-O)₂MoO]₂(渭-OMe)₂ (1), while condensation of Tp^iPrMoO{2-OC₆H₄C(O)Me-魏²O,O鈥瞹 and methylamine gives the chelated iminophenolate complex, Tp^iPrMoO{2-OC₆H₄C(Me)NMe-魏²O,N} (2), rather than the aqua complex, Tp^iPrMoO{2-OC₆H₄C(Me)NMe-魏O}(OH₂). The oxo鈥揗o(IV) complexes are readily oxidized by dioxygen or hydrogen peroxide to the corresponding cis-dioxo鈥揗o(VI) complexes, Tp^iPrMoO₂{2-OC₆H₄C(O)R}; in addition, suitable one-electron oxidants, e.g., [FeCp₂]BF₄ and [N(C₆H₄Br)₃][SbCl₆], oxidize the complexes to their EPR-active (g_iso 鈮?1.942) molybdenyl counterparts (3, 4). Molybdenyl complexes such as Tp^iPrMoOCl{2-OC₆H₄C(O)R} (5) and Tp^iPrMoOCl₂ also form when the complexes react with chlorinated solvents. The ester derivatives (R = OMe, OEt, OPh) react with propylene sulfide to form cis-oxosulfido鈥揗o(VI) complexes, Tp^iPrMoOS{2-OC₆H₄C(O)R}, that crystallize as dimeric 渭-disulfido鈥揗o(V) species, [Tp^iPrMoO{2-OC₆H₄C(O)R}]₂(渭-S₂) (6鈭?b>8). The crystal structures of [Tp^iPrMoO(渭-O)₂MoO]₂(渭-OMe)₂, Tp^iPrMoO{2-OC₆H₄C(Me)NMe}, Tp^iPrMoOCl{2-OC₆H₄C(O)NHPh}路{2-HOC₆H₄C(O)NHPh}, and [Tp^iPrMoO{2-OC₆H₄C(O)R}]₂(渭-S₂) (R = OMe, OEt) are reported.