诸如硅之类的主族元素化合物是绿色且廉价催化剂的诱人候选物。为了使它们与最先进的过渡金属配合物竞争,必须解锁和控制新的反应模式,这可以通过应变来实现。使用三(2-炔基)甲基phosph([TSMPH 3 ] +)支架,我们制备了应变阳离子硅烷[TSMPSiH] +。与一般的氢键Si-H键形成鲜明对比的是,它在4.7–8.1的实验性p K a DMSO中呈酸性,低于苯酚,苯甲酸和少数报道的p K a的氢化硅烷。价值观。我们表明,环应变显着地促进了这种异常的酸度以及感应和静电作用。共轭碱TSMPSi在CH酸存在下活化THF分子,从而通过痕量的[TSMPSiH] +起到释放应变路易斯酸的作用,从而产生高通量的烷氧基硅烷。该反应涉及从Si II到Si IV的正式氧化态变化,与过渡金属介导的过程具有令人着迷的相似性。
The metallotropic η6 ⇌ η5 tautomeric equilibrium in anionic chromium tricarbonyl complexes of fluoradene, substituted fluorenes and indene has been studied. A criterion is proposed for determining the ion-pair type in η6-anions according to the E-band splitting in the ν(CO) region of their IR spectra. The influence of ligand structure and cation solvation on Keq. is discussed.
Solov'yanov, A. A.; Karpyuk, A. D.; Beletskaya, I. P., Journal of Organic Chemistry USSR (English Translation), 1983, p. 1952 - 1963
作者:Solov'yanov, A. A.、Karpyuk, A. D.、Beletskaya, I. P.、Reutov, O. A.
DOI:——
日期:——
Photochemistry of 3H-Indazoles in Protic Media. Benzyl Cations via Protonation of 2-Methylene-3,5-cyclohexadienylidenes
作者:O Fehr
DOI:10.1016/00404-0399(50)1196o-
日期:1995.8.14
FLUORADENE (INDENO[1,2,3-jk]FLUORENE), AN UNUSUALLY ACIDIC HYDROCARBON
作者:H. Rapoport、G. Smolinsky
DOI:10.1021/ja01544a087
日期:1958.6
Stereochemical Inversion of a Coordinated, Curved Hydrocarbon: Syntheses and Structures of <i>e</i><i>xo</i>- and <i>e</i><i>ndo</i>-[Ru(η<sup>6</sup>-fluoradene)(η-C<sub>5</sub>Me<sub>5</sub>)][CF<sub>3</sub>SO<sub>3</sub>]
作者:Aibing Xia、John P. Selegue、Alberto Carrillo、Carolyn P. Brock