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Metathesis between [(Me3Si)2CH)(C6H4-2-OMe)P]K and SmI2(THF)2 in THF yields [([Me3Si]2CH)(C6H4-2-OMe)P)2Sm(DME)(THF)] (1), after recrystallization. A similar reaction between [(Me3Si)2CH)(C6H3-2-OMe-3-Me)P]K and SmI2(THF)2 yields [([Me3Si]2CH)(C6H3-2-OMe-3-Me)P)2Sm(DME)].Et2O (2), while reaction between [(Me3Si)2CH)(C6H4-2-CH2NMe2)P]K and either SmI2(THF)2 or YbI2 yields the five-coordinate complex [([Me3Si]2CH)(C6H4-2-CH2NMe2)P)2Sm(THF)] (3) or the solvent-free complex [([Me3Si]2CH)(C6H4-2-CH2NMe2)P)2Yb] (4), respectively. X-ray crystallography shows that complex 2 adopts a distorted cis octahedral geometry, while complex 1 adopts a distorted pentagonal bipyramidal geometry (1, triclinic, P1, a = 11.0625(9) A, b = 15.924(6) A, c = 17.2104(14) A, alpha = 72.327(2) degrees, beta = 83.934(2) degrees, gamma = 79.556(2) degrees, Z = 2; 2, monoclinic, P2(1), a = 13.176(4) A, b = 13.080(4) A, c = 14.546(4) A, beta = 95.363(6) degrees, Z = 2). Complex 3 crystallizes as monomers with a square pyramidal geometry at Sm and exhibits short contacts between Sm and the ipso-carbon atoms of the ligands (3, monoclinic, C2/c, a = 14.9880(17) A, b = 13.0528(15) A, c = 24.330(3) A, beta = 104.507(2) degrees, Z = 4). Whereas preliminary X-ray crystallographic data for 4 indicate a monomeric structure in the solid state, variable-temperature 1H, 13C(1H), 31P(1H), and 171Yb NMR spectroscopies suggest that 4 undergoes an unusual dynamic process in solution, which is ascribed to a monomer-dimer equilibrium in which exchange of the bridging and terminal phosphide groups may be frozen out at low temperature. 相似文献
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Armstrong DR Clegg W Davies RP Liddle ST Linton DJ Raithby PR Snaith R Wheatley AE 《Angewandte Chemie (International ed. in English)》1999,38(22):3367-3370
Lithium cages containing hydride: The reaction of tBuLi with Me(2)AlN(2-Pyr)Ph in toluene gave [Li(8)(H){N(2-Pyr)Ph}(6)](+)[Li(Me(2)AltBu(2))(2)](-), whose cation is the first molecular main group metal species to contain interstitial hydride (the cluster core is shown in the picture). Treatment of the reaction mixture with THF gave the neutral hydride Li(7)(H)[N(2-Pyr)Ph](6), which has a capped octahedral (Li(+))(7) cluster core. 2-Pyr=2-pyridyl. 相似文献
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Arnold PL Zlatogorsky S Jones NA Carmichael CD Liddle ST Blake AJ Wilson C 《Inorganic chemistry》2008,47(19):9042-9049
The d (0) yttrium N-heterocyclic carbene compound YL 3 (L = OCMe 2CH 2[C{N(CHCH)NPr ( i )}]) has been made and structurally characterized. It adopts a mer configuration of the three bidentate ligands. A comparison of this with the isostructural d (1) titanium complex TiL 3 is made in order to seek experimental evidence of a pi-bonding contribution to the M-C bond. This has been augmented by DFT calculations. Experimentally, the metal radius-corrected Ti-C distance is shorter than the Y-C distance, suggesting a pi-bonding contribution in the d (1) complex, but the computational data suggest that a shorter sigma bond might simply be formed by the more strongly polarizing titanium cation. From the potassium reduction of TiL(OPr ( i )) 3, only a byproduct arising from silicone grease activation was isolable, identified as a mixed-valent, multinuclear, d (0)/d (1) cluster [Ti (III)L 2{Pr ( i )OSiMe 2O}K 2OTi (IV)(OPr ( i )) 4] 2 in which the carbene ligands are bound to the Ti (III) centers in preference to Ti (IV), with longer Ti-C distances than those found in TiL 3. 相似文献
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电感耦合等离子体原子发射光谱法测定钛酸钡纳米粉体中7种杂质元素 总被引:3,自引:0,他引:3
钛酸钡纳米粉体样品用盐酸溶解,在所得样品溶液中用电感耦合等离子体原子发射光谱法测定了以氧化物存在于样品中的7种杂质元素(包括镁、锶、钾、钠、铝、硅及铁),对测定的光谱条件进行了试验并优化达到上述各元素的测定上限为0.1%(质量分数).测得方法的检出限(3S/b)为(单位μg·L-1):2.0(铝),1.0(铁),20.0(钾),0.2(镁),4.0(钠),3.0(硅)及0.5(锶).应用此方法分析了两件实样,所得结果的相对标准偏差(n=6)小于等于2.0%,对其中4种杂质元素(镁、钾、钠和锶)同时用HG/T 3587-1999标准中的方法作分析校核,所得结果与此方法结果一致. 相似文献
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Actinide–Pnictide (An−Pn) Bonds Spanning Non‐Metal,Metalloid, and Metal Combinations (An=U,Th; Pn=P,As, Sb,Bi)
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Thomas M. Rookes Dr. Elizabeth P. Wildman Dr. Gábor Balázs Dr. Benedict M. Gardner Dr. Ashley J. Wooles Dr. Matthew Gregson Dr. Floriana Tuna Prof. Dr. Manfred Scheer Prof. Dr. Stephen T. Liddle 《Angewandte Chemie (International ed. in English)》2018,57(5):1332-1336
The synthesis and characterisation is presented of the compounds [An(TrenDMBS){Pn(SiMe3)2}] and [An(TrenTIPS){Pn(SiMe3)2}] [TrenDMBS=N(CH2CH2NSiMe2But)3, An=U, Pn=P, As, Sb, Bi; An=Th, Pn=P, As; TrenTIPS=N(CH2CH2NSiPri3)3, An=U, Pn=P, As, Sb; An=Th, Pn=P, As, Sb]. The U?Sb and Th?Sb moieties are unprecedented examples of any kind of An?Sb molecular bond, and the U?Bi bond is the first two‐centre‐two‐electron (2c–2e) one. The Th?Bi combination was too unstable to isolate, underscoring the fragility of these linkages. However, the U?Bi complex is the heaviest 2c–2e pairing of two elements involving an actinide on a macroscopic scale under ambient conditions, and this is exceeded only by An?An pairings prepared under cryogenic matrix isolation conditions. Thermolysis and photolysis experiments suggest that the U?Pn bonds degrade by homolytic bond cleavage, whereas the more redox‐robust thorium compounds engage in an acid–base/dehydrocoupling route. 相似文献
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