Reactivity Studies of a T‑Shaped Yttrium Carbene: C–F and C–O Bond Activation and CC Bond Formation Promoted by [Y(BIPM)(I)(THF)2] (BIPM = C(PPh2NSiMe3)2)
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The yttrium carbene complex [Y(BIPM)(I)(THF)2] (1; BIPM = C(PPh2NSiMe3)2) was reacted with a range of unsaturated substrates. The reaction of 1 with the phosphaalkyne PCBut afforded the [2 + 2] cycloaddition product [Y{C(PPh2NSiMe3)2(PCBut)-κ4C,C′,N,N′}(I)] (2). Similarly, the reactions of 1 with the heteroallenes N,N′-dicyclohexylcarbodiimide and tert-butyl isocyanate gave the [2 + 2] cycloaddition products [Y{C(PPh2NSiMe3)2[C(NCy)2]-κ4C,N,N′,N″}(I)(THF)] (3) and [Y{C(PPh2NSiMe3)2[C(O)(NBut)]-κ4C,N,N′,O}(I)(THF)2] (4), respectively. In contrast, the reaction of 1 with tert-butyl isothiocyanate afforded the ketenimine ButNCC(PPh2NSiMe3)2 (5), with the concomitant formal elimination of “YSI(THF)n”. The sterically demanding arylamine 2,6-diisopropylphenylamine reacted with 1 via a 1,2-addition across the YC bond to yield the anilide–methanide complex [Y(BIPMH)(NHDipp)(I)(THF)] (6; Dipp = C6H3Pri2-2,6). The reaction of 1 with the benzopyrone coumarin affords the ring-opened dinuclear aryloxide–enolate complex [Y2{C(PPh2NSiMe3)2[C(O)(CHCHC6H4O-2)]-κ2-N,O:μ,κ-O′}2(I)(μ-I)(THF)] (7), which is postulated to form by sequential Y–O, C–C, and CC bond formation and cleavage of the C–O ester linkage and the CO and YC double bonds. Benzoyl fluoride reacts with 1 to afford 1/2 equiv of the bis-enolate complex [Y{C(PPh2NSiMe3)2[C(O)(Ph)]-κ2N,O}2(I)] (8) with formal elimination of “YF2I(THF)n” by ligand scrambling. Complexes 2–8 have been characterized by X-ray crystallography, multielement NMR spectroscopy, FTIR spectroscopy, and CHN microanalyses.
创建时间：
2016-02-19
