Backbone Reactivity of Lithium β-Diketiminate (NacNac) Complexes with CO2, tBuNCO and iPrNCO

Though alkali metal NacNac (β-diketiminate) complexes have been utilised in synthesis as NacNac-transfer agents, studies of them in their own right with small molecules are exceptionally rare. Here, the lithium compound of the common 2,6-diisopropylphenyl-β-methyldiketiminate [NacNac(Dipp, Me)] ligand is investigated with carbon dioxide and isocyanates. In all four cases reaction occurs at the backbone γ-C atom of the NacNac ligand, which redistributes electronically into a diimine. Insertion of CO₂ gives an eight-atom carboxylate (Li₂O₄C₂) ring at the γ-C site in a dimer. Insertion of tBuNCO gives a secondary amide at the γ-C site in a monomer with TMEDA chelating lithium. Double insertion of tBuNCO and (adventitious) oxygen gives a dimer with a (LiO)₂ central core involving the latter source. Insertion of less bulky (iPrNCO) gives a dimer with dimerisation through the C=O bonds of the emergent secondary amide function.     

A monomeric three-coordinate magnesium bis(amide)

The metallation reaction between di­butyl­magnesium and 2,6-diiso­propyl-N-(tri­methyl­silyl)­aniline gives the unusual monomeric three-coordinate complex (diethyl ether-κO)­bis­[2,6-diiso­propyl-N-(tri­methyl­silyl)­anilido-κN]­magnesium(II), [Mg(C₁₅H₂₆NSi)₂(C₄H₁₀O)] or [Mg{(Me₃Si)(2,6-ⁱPr₂C₆H₃)N}₂(Et₂O)]. This low-coordinate species has a distorted trigonal-planar coordination environment, with an additional short Mg—C_ipso contact of 2.799 (2) Å.     

共振辐射的理论研究——Holstein方程的解

解决介质中共振辐射的关键问题是求解Holstein方程。本文直接利用算符运算将方程积分,给出了激发态粒子集居数的含无限项的级数表达式。基于对这个级数高阶系数的极限行为的研究,成功地克服了无穷项求和的困难,整理出一个在任意给定精度下都只含有限项的解式,由它可以计算出任何时刻的结果。 关键词：     

壳聚糖膜固定生物活性短肽RGDS的研究

为改善壳聚糖对细胞的特异性吸附,采用水溶性碳二亚胺将生物活性短肽精氨酸-甘氨酸-天冬氨酸-丝氨酸(RGDS)固定到壳聚糖膜的表面,采用X射线光电子能谱检测固定多肽前后的壳聚糖膜表面,发现反应后壳聚糖膜表面氮元素含量增大,Nls和Cls曲线拟合谱中酰胺键增多,表明RGDS短肽已固定到壳聚糖膜的表面;人角膜缘上皮细胞体外培养实验表明,固定RGDS后壳聚糖膜的细胞黏附率有了明显提高,固定RGDS后的壳聚糖膜在角膜组织工程支架等方面有更好的应用潜力。     

Direct C?H Metalation with Chromium(II) and Iron(II): Transition‐Metal Host / Benzenediide Guest Magnetic Inverse‐Crown Complexes

Check M(etal)ate: The chessboard and the figures represent a special reaction in which different low‐polarity metals can metalate arenes directly when they are brought into the right position. In a combination of queen (sodium) and knight (chromium or iron), it is possible for the knight (usually the weaker piece) to make a direct deadly hit on the king (benzene) in this game of elemental chess.

     

Single electron transfer (SET) activity of the dialkyl-amido sodium zincate [(TMEDA)·Na(μ-TMP)(μ-tBu)Zn(tBu)] towards TEMPO and chalcone

More usually thought of as a base, the sodium zincate [(TMEDA)·Na(μ-TMP)(μ-(t)Bu)Zn((t)Bu)] 1 can undergo single electron transfer with TEMPO to give [(TMEDA)·Na(μ-TMP)(μ-TEMPO(-))Zn((t)Bu)] 2 and [(TMEDA)·Na(μ-TEMPO(-))(2)Zn((t)Bu)] 3; and with chalcone [PhCOCH=CHPh] gives [{(TMEDA)·Na(μ-TMP)Zn((t)Bu)}(2)(μ-OCPhCH=CHPhCHPhCH=CPh-μ-O)] which contains two chalcone units C-C coupled though their benzylic C atoms.     

New reactivity and structural insights of alkali-metal-mediated alumination in directed ortho-alumination of a tertiary aromatic amide

The first reported sodium alkyl(TMP)aluminate reagent to be synthesised and crystallographically characterised, [TMEDA.Na(mu-TMP)(mu-(I)Bu)Al((I)Bu)2], reacts as an amido base towards phenylacetylene to form crystalline [(TMEDA)2.Na(mu-CCPh)(mu-(I)Bu)Al((I)Bu)2]; whereas the congeneric TMEDA-stabilised lithium (TMP)aluminate exhibits dual alkyl/amido basicity in its reaction with N,N-diisopropylbenzamide to form a novel heterobimetallic-heterotrianionic crystalline complex [{PhC(=O)N(iPr)2}.Li{2-[1-C(=O)N(iPr)2]C6H4}{Me2NCH2CH2N(Me)CH2}Al(iBu)2], which, in addition to having an ortho-deprotonated benzamide ligand, also contains a methyl-deprotonated TMEDA ligand and a neutral benzamide molecule ligated to lithium.