Reactivity Studies of Oxo–Mo(IV) Complexes Containing Potential Hydrogen-Bond Acceptor/Donor Phenolate Ligands
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Reactivity studies of oxo–Mo(IV) complexes, TpiPrMoO{2-OC6H4C(O)R-κ2O,O′} (R = Me, Et, OMe, OEt, OPh, NHPh), containing chelated hydrogen-bond donor/acceptor phenolate ligands are reported. Hydrolysis/oxidation of TpiPrMoO(2-OC6H4CO2Ph-κ2O,O′) in the presence of methanol yields tetranuclear [TpiPrMoO(μ-O)2MoO]2(μ-OMe)2 (1), while condensation of TpiPrMoO{2-OC6H4C(O)Me-κ2O,O′} and methylamine gives the chelated iminophenolate complex, TpiPrMoO{2-OC6H4C(Me)NMe-κ2O,N} (2), rather than the aqua complex, TpiPrMoO{2-OC6H4C(Me)NMe-κO}(OH2). The oxo–Mo(IV) complexes are readily oxidized by dioxygen or hydrogen peroxide to the corresponding cis-dioxo–Mo(VI) complexes, TpiPrMoO2{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 (giso ≈ 1.942) molybdenyl counterparts (3, 4). Molybdenyl complexes such as TpiPrMoOCl{2-OC6H4C(O)R} (5) and TpiPrMoOCl2 also form when the complexes react with chlorinated solvents. The ester derivatives (R = OMe, OEt, OPh) react with propylene sulfide to form cis-oxosulfido–Mo(VI) complexes, TpiPrMoOS{2-OC6H4C(O)R}, that crystallize as dimeric μ-disulfido–Mo(V) species, [TpiPrMoO{2-OC6H4C(O)R}]2(μ-S2) (6−8). The crystal structures of [TpiPrMoO(μ-O)2MoO]2(μ-OMe)2, TpiPrMoO{2-OC6H4C(Me)NMe}, TpiPrMoOCl{2-OC6H4C(O)NHPh}·{2-HOC6H4C(O)NHPh}, and [TpiPrMoO{2-OC6H4C(O)R}]2(μ-S2) (R = OMe, OEt) are reported.
