首页> 外文期刊>Organometallics >Synthesis, characterization, and reactivity of niobium and tantalum complexes bearing metal-nitrogen bonds. X-ray molecular structure of [Nb(C5H4SiMe3){NH(CH2)(2)-eta-NH2}Cl-3] and the novel tetranuclear niobium oxo derivative [{Nb(C5H4SiMe3)Cl( mu(2
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Synthesis, characterization, and reactivity of niobium and tantalum complexes bearing metal-nitrogen bonds. X-ray molecular structure of [Nb(C5H4SiMe3){NH(CH2)(2)-eta-NH2}Cl-3] and the novel tetranuclear niobium oxo derivative [{Nb(C5H4SiMe3)Cl( mu(2

机译:铌和钽络合物轴承金属氮键的合成,表征和反应性。 [Nb(C5H4Sime3){NH(CH2)(2)-etA-NH2} Cl-3]的X射线分子结构和新的四核铌氧代衍生物[{Nb(C5H4Sime3)Cl(mu(2

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摘要

The reaction of the cyclopentadienyl-silyl-amido titanium compound [Ti{eta(5)-C5H4SiMe2-eta-N(CH2)(2)-eta-NH2}Cl-2] with group 5 metal monocyclopentadienyl complexes [(MCpCl4)-Cl-R] (M = Nb, Ta; Cp-R = C5H4-SiMe3 (CP'), C5Me5 (Cp*)) afforded the heterobimetallic complexes [TiCl2{eta(5)-C5H4SiMe2-eta-N(CH2)(2)-kappa-NH2}MCp Cl-R(4)] (M = Nb, Cp-R = Cp', 2a; Cp*, 2b; M = Ta, Cp-R = Cp', 3a; Cp = Cp*, 3b). Compounds 2 evolve at room temperature to give a three-component mixture, the chlorosilyl-substituted cyclopentadienyl titanium compound [Ti(eta(5)-C5H4SiMe2CI)Cl-3], the corresponding mononuclear amido-amino, [NbCpR{NH(CH2)(2)-eta-NH2}Cl-3] (Cp-R = Cp', 4a; Cp*, 4b), and the dinuclear imido niobium complexes [{(NbCpCl2)-Cl-R}(2)(mu-N(CH2)(2)-eta-N)] (Cp-R = Cp', 5a; Cp*, 5b). In contrast, the analogue tantalum complexes thermally degraded, when CpR = Cp' at normal temperature, whereas when CpR = Cp* at temperatures higher than 50 degrees C, they gave a unique tantalum complex, the corresponding mononuclear amido-amino derivative [TaCpR{NH(CH2)(2)-eta-NH2}Cl-3] (Cp-R = Cp', 6a; Cp*, 6b). Alternatively, these group 5 complexes were prepared by direct reaction of the monocyclopentadienyl derivatives with the corresponding organic diamine, in the appropriate proportion and reaction conditions. Tantalum amino adducts were observed as intermediate species in the course of such reactions, and even the dinuclear derivative [{TaCp*Cl-4}(2)(mu-NH2(CH2)(2)NH2)] (8) could be isolated. Hydrolysis of the dinuclear imido complex 5a yielded the tricyclic tetranuclear niobium oxo derivative [{NbCp'Cl(mu(2)-O)}(4)(Cl)(2)(mu(3)-O)] (9), which displays an asymmetrical structure as a consequence of the triply connected oxygen site. These compounds were characterized by elemental analysis and NMR spectroscopy, and the crystal structures of 4a and 9 were determined by X-ray diffraction methods.
机译:环戊二烯基甲硅烷基酰氨基钛化合物的反应钛[Ti {(5)ETA -C5H4SiMe2-ETA-N(CH 2)(2)-ETA-NH 2} CL-2]与第5种族金属的单环戊二烯配合物[(MCpCl4) - CL-R](M =铌,钽CP-R = C5H4-SiMe3,C5Me5(CP *)(CP')),得到双核配合物[{生成TiCl2 ETA(5)-C5H4SiMe2-ETA-N(CH 2)( 2)-κ-NH 2} MCP CL-R(4)](M =铌,CP-R = CP '2a中; *的Cp,2B; M =钽,CP-R = CP',3A; CP =的Cp *,3B)。化合物2在演变室温,得到的三组分混合物中,氯甲硅烷取代的环戊二烯钛化合物钛[Ti(ETA(5)-C5H4SiMe2CI)CL-3],相应的单核酰氨基 - 氨基,[NbCpR {NH(CH 2) (2)-ETA-NH 2} CL-3](CP-R = CP”,4A;的Cp *,4B),和双核酰亚胺铌配合物[{(NbCpCl2)-Cl-R}(2)(亩N(CH 2)(2)-ETA-N)](CP-R = CP”,5A;的Cp *,5B)。与此相反,模拟钽配合物热降解,当的Cp = CP”在常温下,而当的Cp =的Cp *在温度高于50度C时,它们给予了独特的钽复杂,相应的单核酰氨基 - 氨基衍生物[TaCpR { NH(CH 2)(2)-ETA-NH 2} CL-3](CP-R = CP”,6A;的Cp *,6B)。可替代地,通过用相应的有机二胺单环戊二烯基衍生物的直接反应来制备这些组5复合物,在适当的比例和反应条件。钽氨基加合物,观察到作为中间物质在这些反应的过程中,甚至双核衍生物[{TACP * CL-4}(2)(MU-NH 2(CH 2)(2)NH 2)](8)可被分离。双核酰亚胺复合物5a的水解,得到三环四环铌氧代衍生物[{NbCp'Cl(亩(2)-O)} ...(4)(CL)(2)(亩(3)-O)](9),其中显示的非对称结构的三重连接氧位的结果。这些化合物经元素分析和NMR光谱4a的晶体结构,其特征在于,与和9通过X射线衍射方法测定的。

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