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• W2289802916 endingPage "43" @default.
• W2289802916 startingPage "31" @default.
• W2289802916 abstract "The syntheses and reactivities of tantalum alkyl, hydride, and silyl complexes containing a sterically demanding, mixed Cp*-(terphenyl)imido (Cp* = η5-C5Me5) ligand set are reported. The dichloride complex Cp*(ArMesN)TaCl2 (1), prepared by the reaction of ArMesNHLi (ArMes = 2,6-(2,4,6-Me3C6H2)2C6H3) with Cp*TaCl4 in the presence of a large excess of NEt3, was structurally characterized. Complex 1 reacted readily with KSi(SiMe3)3 to give the silyl chloride compound Cp*(ArMesN)Ta[Si(SiMe3)3]Cl (2), and with MeLi (2 equiv) to yield the dimethyl complex Cp*(ArMesN)TaMe2 (4). Compound 2 reacted with PhSiH3 via the intermediate complex Cp*(ArMesN)Ta(SiH2Ph)Cl to give the hydrido chloride complex Cp*(ArMesN)Ta(H)Cl (3). While the analogous compound of the [DippN]2- (Dipp = 2,6-iPr2C6H3) ligand is a dimer with bridging hydrides, compound 3 contains a terminal hydride, as indicated by the downfield 1H NMR resonance of the hydride ligand (15.28 ppm). Treatment of 4 with AgOTf (OTf = OSO2CF3) provided the methyl triflate compound Cp*(ArMesN)Ta(Me)OTf (6), which reacted cleanly with H2 in bromobenzene to yield pale yellow crystals of the hydrido triflate complex Cp*(ArMesN)Ta(H)OTf (7). Complexes 4, 6, and 7 reacted with PhSiH3 at high temperatures (85−100 °C) to give silane products arising from σ-bond metathesis and redistribution of the substituents at silicon. The neopentyl hydride complex Cp*(ArMesN)Ta(CH2CMe3)H (8), prepared by treating 7 with LiCH2CMe3, reacted with PhSiH3 at room temperature via the silyl hydride intermediate species Cp*(ArMesN)Ta(SiH2Ph)H to yield the dihydride dimer [Cp*(ArMesN)TaH(μ-H)]2 (5). In an effort to stabilize a monomeric dihydride complex, the more sterically demanding [ArTripN]2- (ArTrip = 2,6-(2,4,6-iPr3C6H2)2C6H3) ligand was employed. The dichloride complex Cp*(ArTripN)TaCl2 (12) and the dimethyl complex Cp*(ArTripN)TaMe2 (13) were prepared using procedures analogous to those used for the syntheses of 1 and 4. Treatment of 13 with H2 in bromobenzene yielded the hydrido bromide complex Cp*(ArTripN)Ta(H)Br (14), which formed via solvent activation by the intermediate dihydride species Cp*(ArTripN)TaH2. When D2 was used in place of H2, Cp*(2-[2-(iPr-d6)-4,6-iPr2C6H2]-6-Trip-C6H3N)Ta(D)Br (14-d7, Trip = 2,4,6-iPr3C6H2) was obtained. Compound 14-d7 arises from the intramolecular C−H bond activation of the methyl groups of one of the isopropyl substituents of the [ArTripN]2- ligand. Hydrogenolysis of the neopentyl hydride complex Cp*(ArTripN)Ta(CH2CMe3)H (15) in bromobenzene-d5 allowed observation of the corresponding dihydride complex, which was observed to slowly convert to the hydrido bromide species 14." @default.
• W2289802916 created "2016-06-24" @default.
• W2289802916 creator A5009353166 @default.
• W2289802916 creator A5079726681 @default.
• W2289802916 date "2003-12-06" @default.
• W2289802916 modified "2023-09-23" @default.
• W2289802916 title "Synthesis and Reactivity of Alkyl, Hydride, and Silyl Derivatives of the (Terphenyl)imido Fragments Cp*(Ar^MesN)Ta (Cp* = η⁵-C₅Me₅; Ar^Mes = 2,6-(2,4,6-Me₃C₆H₂)₂C₆H₃) and Cp*(Ar^TripN)Ta (Ar^Trip = 2,6-(2,4,6-ⁱPr₃C₆H₂)₂C₆H₃)" @default.
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• W2289802916 doi "https://doi.org/10.1021/om030567z" @default.
• W2289802916 hasPublicationYear "2003" @default.
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