2017
DOI: 10.1021/acs.inorgchem.7b01652
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An Effective Route to Dinuclear Niobium and Tantalum Imido Complexes

Abstract: Thermal treatment of the trichloro complexes [MCl(NR)py] (R = tBu, Xyl; M = Nb, Ta) (Xyl = 2,6-MeCH) under vacuum affords the dinuclear imido species [MCl(μ-Cl)(NR)py] (R = tBu, Xyl; M = Nb 1, 3; Ta 2, 4) with loss of pyridine. Complexes 1-4 can be easily transformed to the mononuclear starting materials [MCl(NR)py] (R = tBu, Xyl; M = Nb, Ta) upon reaction with pyridine. While reactions of compounds 1 and 2 with a series of alkylating reagents render the mononuclear peralkylated imido complexes [MR(NtBu)] (R =… Show more

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Cited by 10 publications
(4 citation statements)
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“…Another strategy is to use inner-sphere reductants that are less prone to over-reduction. In this context, Tsurugi and Mashima have promoted the use of organosilicon reductants, such as 3,6-bis(trimethylsilyl)-1,4-cyclohexadiene 6668 ( 7 ) and 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine 6971 derivatives (for example, 8 ), to reduce group 4 and group 5 metal halides (Fig. 2c) for homogeneous catalytic applications.…”
Section: Generation Of Low-valent Complexesmentioning
confidence: 99%
“…Another strategy is to use inner-sphere reductants that are less prone to over-reduction. In this context, Tsurugi and Mashima have promoted the use of organosilicon reductants, such as 3,6-bis(trimethylsilyl)-1,4-cyclohexadiene 6668 ( 7 ) and 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine 6971 derivatives (for example, 8 ), to reduce group 4 and group 5 metal halides (Fig. 2c) for homogeneous catalytic applications.…”
Section: Generation Of Low-valent Complexesmentioning
confidence: 99%
“…Complexes 6 and 7 were obtained as a white crystalline powder and purified via recrystallization from a saturated toluene solution at −30 °C. The reaction between the imido group and water is well known in numerous studies. Complexes 6 and 7 were characterized by 1 H NMR spectroscopy, EA, FT-IR, and single-crystal X-ray analysis (Tables S1 and S2 and Figures S13–S16 and ). The 1 H NMR spectrum of complex 6 showed only edpa ligand peaks at 0.90 (s, 9H, CC­(C H 3 ) 3 ), 1.05 (t, 3H, OCH 2 C H 3 ), and 3.76 ppm (q, 2H, OC H 2 CH 3 ).…”
Section: Resultsmentioning
confidence: 99%
“…We then examined the reduction of some imido chloride complexes of group 5 and 6 metals, as low-valent early transition metal complexes bearing an imido ligand have attracted much interest because of their strong electron-donating nature . When ( t BuN)­NbCl 3 (py) 2 was treated with 2c in toluene at room temperature, chloride-bridged dinuclear niobium­(IV) complex 29 was obtained as a poorly soluble purple precipitate together with 1 equiv of ClSiMe 3 and 0.5 equiv of Me 4 pyrazine . On the other hand, the reaction with non-methylated reductant 2a afforded Nb­(V) complex 30 with the formation of 1 equiv of ClSiMe 3 , as summarized in Scheme .…”
Section: Reduction Of Early Transition Metal Complexes With Electron-...mentioning
confidence: 99%