Syntheses and structures of zinc and tin(II) compounds with hemilabile N-silyl-tert-butylamido and N-silyl-p-tolylamido ligands that contain pendent tert-butoxy groups
摘要:
Syntheses and solid-state structures of zinc and tin(II) compounds, containing the N-silyl-amide ligands ((OBu)-Bu-t)(NR)SiMe2, R = Bu-t (L-tBu), or R = p-tolyl (L-pTol), are reported. The N-silyl amines were synthesized by modified published procedures from commercially available Me2SiCl2, (BuOH)-Bu-t, and (BuNH2)-Bu-t, or p-Me-C6H4NH2, respectively. Treatment of SnCl2 with LiLpTol furnished Sn(L-pTol)(2), which was X-ray structurally characterized and shown to contain two covalent Sn-N bonds and two asymmetrical O -> Sn donor bonds. The single-crystal X-ray structure of Sn(L-tBu)(2) revealed a much more symmetrically-coordinated, pseudo-trigonal-bipyramidal tin atom. Aminolysis of diethylzinc with HLpTol produced [EtZn(L-pTol)](2) which crystallized as a centrosymmetric dimer, containing four-coordinate zinc atoms connected by bridging amides. Zinc dichloride, by contrast, reacted with two equivalents of LiLtBu to produce the homoleptic, pseudo-spirocyclic Zn(L-tBu)(2). (C) 2011 Elsevier Ltd. All rights reserved.
Di(alkylamido)zirconium dichlorides and tri(arylamido)zirconium monochlorides having hemilabile N, O ligands and their methyl derivatives
作者:Gregory L. Fondong、Edmond Y. Njua、Lothar Stahl
DOI:10.1016/j.jorganchem.2014.11.012
日期:2015.1
potential use in the polymerization of α-olefins, secondary amides with pendent N-tert- butyoxydimethylsilyl groups and some of their zirconium complexes were synthesized. Treatment of cis-ZrCl4(THF)2 with LiLtBu, where LtBu is the anion of the mixed N, O-donor ligand Me2Si(OtBu) (NHtBu), gave cis-(LtBu)2ZrCl2. A single-crystal X-ray analysis revealed a pseudo-octahedral zirconiumcenter with two chlorides
对于他们的α烯烃的聚合中的潜在用途,具有侧仲酰胺ñ -叔- butyoxydimethylsilyl基团以及它们的一些锆络合物的合成。用LiL tBu处理顺式-ZrCl 4(THF)2,其中L tBu是混合的N,O-供体配体Me 2 Si(O t Bu)(NH t Bu)的阴离子,得到顺式-(L tBu)2氯化锆2。单晶X射线分析显示伪八面体锆中心具有两个氯化物和两个螯合的N,O配体。用对甲苯胺或对茴香胺取代叔丁胺可提供空间较小的Me 2 Si(O t Bu)(NH- p -C 6 H 4 Me)= HL pTol和Me 2 Si(O t Bu)(NH - p -C 6 H ^ 4 OME)= HL潘尼斯,分别。顺式-ZrCl 4(THF)的反应2与两个当量的LiL pTol或LiL pAnis始终不变地分别仅给出三酰氨基-一氯代配合物(L pTol)3 ZrCl和(L pAnis)3 Z
Si-O-Bindungsspaltung in einem Siloxamin durch Aluminiumhydrid
Setzt man das Alkoxyaminosilan tBu-O[tBuN(H)]SiMe2 (1) mit Aluminiumhydrid um, so isoliert man nicht das erwartete cyclische Alkoxyaluminosiloxan tBuO(tBuN)(AlH2)SiMe2 (2). Statt dessen reagiert 1 mit zwei Aquivalenten Aluminiumhydrid zum Alkoxyaminodialan 3, (tBuO)(AlH2)[N(SiMe2H)tBu](AlH2). Die Verbindung 3 kann uber spektroskopische Methoden und uber eine Einkristallrontgenstrukturanalyse zweifelsfrei
Setzt man das Alkoxyaminosilan tBu-O[tBuN(H)]SiMe2 (1) mit Aluminiumhydrid um, so isoliert man nicht das erwartete cyclische Alkoxyaluminosiloxan tBuO(tBuN)(AlH2)SiMe2 (2)。Stat dessen reagiert 1 mit zwei Aquivalenten Aluminiumhydrid zum Alkoxyaminodialan 3, (tBuO)(AlH2)[N(SiMe2H)tBu](AlH2)。Die Verbindung 3 kann uber spektroskopische Methoden und uber eine Einkristallrontgenstrukturanalysis zweifelsfrei
Darstellung einer molekularen, monomeren thallium(I)-Verbindung mit einem neuen chelatisierenden Liganden
作者:M. Veith、R. Rösler
DOI:10.1016/s0022-328x(00)90276-6
日期:1982.4
the synthesis of some metal derivatives. With n-butyllithium III forms [Me2Si(Me3CO)(Me3CNLi)]2 (IV), which is found to be dimeric in solution and in the gas phase. When IV is allowed to react with thallium(I) chloride in diethyl ether the monomeric, highly reactive Me2Si- (Me3C) (II) is formed under precipitation of lithium chloride. The cyclic structure and the physical properties of II can be understood