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首页> 外文期刊>Organometallics >Synthesis, Structural Characterization, and Reactivity of Rare-Earth Complexes Derived from A New Phosphorus-Bridged Versatile Ligand,~iPr_2NP(C_9H_7)(C_2B_(10)H_(11))
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Synthesis, Structural Characterization, and Reactivity of Rare-Earth Complexes Derived from A New Phosphorus-Bridged Versatile Ligand,~iPr_2NP(C_9H_7)(C_2B_(10)H_(11))

机译:新型磷桥杂配体〜iPr_2NP(C_9H_7)(C_2B_(10)H_(11)衍生的稀土配合物的合成,结构表征和反应活性

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摘要

New phosphorus-bridged ligands incorporating both indenyl and carboranyl moieties were prepared. Reaction of ~iPr_2NP(C_9H_7)Cl (1) with 1 equiv of Li_2C_2B_(10)H_(11) gave, after treatment with 1 equiv of n-BuLi, the dilithium salt [~iPr_2NP(C_9H_6)(C_2B_(10)H_(10))]Li_2(OEt_2)_(1.5) (2). 2 can be conveniently converted into its neutral counterpart ~-Pr_2NP(C_9H_7)(C_2B_(10)H_(11)) (4) by treatment with excess dry Me_3NHCl in CH_2Cl_2. Mixing 2 and 4 in a 1:1 molar ratio afforded quantitatively the monolithium salt [~iPr_2NP(C_9H_6)(C_2B_(10)H~(11))]Li(DME)_3 (3). Reaction of YbI_2 with 1 equiv of 2 gave the organoytterbium(II) complex [eta~5:sigma-~iPr_2NP(C_9H_6)(C_2B_(10)H_(10))]Yb-(DME)_2 (5). 5 reacted further with 1 equiv of 3 to afford the organoytterbium(III) complex [{eta~5:sigma-~iPr_2NP(C_9H_6)(C_2B_(10)H_(10))}_2Yb][Li(THF)_3(Et_2O)] (6). In sharp contrast, treatment of SmI_2 with 1 equiv of 2 generated the trivalent organosamarium complex [{eta~5:sigma-~iPr_2NP(C_9H_6)-(C_2B_(10)H_(10))}_2Sm][Li(DME)_3] (7). Reaction of LnCl_3 with 2 equiv of 2 gave the ionic complexes [{eta~5:sigma~iPr_2NP(C9H_6)(C_2B_(10)H_(10))}_2Ln][Li(L_1)_nL_2]] (Li = L_2 = DME, n = 2, Ln=Sm (7), Nd (8), Er (9); L_1 = DME, L_2 = THE, n = 2, Ln = Y (10)). Reaction between equimolar amounts of LnCl_3 and 2 resulted in the isolation of the lanthanocene chlorides [{[eta~5:sigma-~iPr_2NP(C_9H_6)-(C_2B_(10)H_(10))]LnCl}_2(mu-Cl)_3Li(DME)][Li(DME)_3]_2 (Ln = Er (11), Y (12)). The chloro groups in these complexes can be replaced by other moieties. For example, reaction of 12 with 2 equiv of KCH2Ph afforded the unexpected compound {[eta~5:sigma-~iPr_2NP(C_9H_6)(C_2B_(10)H_(10))]_2Y}{(eta~6-C_6H_5-CH_3)_2K} (13) and treatment of 12 with 2 equiv of NaBH_4 produced the organoyttrium hydrides [{eta~5:sigma-~iPr_2NP(C_9H_6)(C_2B_(10)H_(10))}Y{(mu-H)_3BH}_2][Li(DME)_3] (14). All complexes were fully characterized by various spectroscopic techniques and elemental analyses. The structures of some of the compounds were further confirmed by single-crystal X-ray analyses.
机译:制备了结合有茚基和碳硼烷基部分的新的磷桥联配体。 〜iPr_2NP(C_9H_7)Cl(1)与1当量的Li_2C_2B_(10)H_(11)反应,在用1当量的n-BuLi处理后得到二锂盐[〜iPr_2NP(C_9H_6)(C_2B_(10)H_ (10))] Li_2(OEt_2)_(1.5)(2)。通过在CH_2Cl_2中用过量的干燥Me_3NHCl处理,可以方便地将2转化为其中性对应物〜-Pr_2NP(C_9H_7)(C_2B_(10)H_(11))(4)。将2和4以1:1的摩尔比混合,定量得到单锂盐[〜iPr_2NP(C_9H_6)(C_2B_(10)H〜(11))] Li(DME)_3(3)。 YbI_2与1当量的2反应生成有机y(II)络合物[η〜5:sigma-iPr_2NP(C_9H_6)(C_2B_(10)H_(10))] Yb-(DME)_2(5)。 5与1当量3进一步反应,得到有机y(III)络合物[{eta〜5:sigma-〜iPr_2NP(C_9H_6)(C_2B_(10)H_(10))} _ 2Yb] [Li(THF)_3(Et_2O) )](6)。与之形成鲜明对比的是,用1当量的2处理SmI_2产生了三价有机sa络合物[{eta〜5:sigma-〜iPr_2NP(C_9H_6)-(C_2B_(10)H_(10))} _ 2Sm] [Li(DME)_3 ](7)。 LnCl_3与2当量的2反应生成离子络合物[{eta〜5:sigma〜iPr_2NP(C9H_6)(C_2B_(10)H_(10))} _ 2Ln] [Li(L_1)_nL_2]](Li = L_2 = DME,n = 2,Ln = Sm(7),Nd(8),Er(9); L_1 = DME,L_2 = THE,n = 2,Ln = Y(10))。等摩尔量的LnCl_3与2之间的反应导致分离出镧系元素氯化物[{[eta〜5:sigma-〜iPr_2NP(C_9H_6)-(C_2B_(10)H_(10))] LnCl} _2(mu-Cl) _3Li(DME)] [Li(DME)_3] _2(Ln = Er(11),Y(12))。这些配合物中的氯基可以被其他部分取代。例如,将12与2当量的KCH2Ph反应得到意外化合物{[eta〜5:sigma-〜iPr_2NP(C_9H_6)(C_2B_(10)H_(10))] _ 2Y} {(eta〜6-C_6H_5-CH_3 )_2K}(13)并用2当量的NaBH_4处理12产生有机钇氢化物[{eta〜5:sigma-〜iPr_2NP(C_9H_6)(C_2B_(10)H_(10))} Y {(mu-H) _3BH} _2] [Li(DME)_3](14)。所有配合物均通过各种光谱技术和元素分析得到充分表征。通过单晶X射线分析进一步证实了某些化合物的结构。

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