X-ray analysis of the first trigermaallene (3) and 1,3-digermasilaallene (4) revealed that the trimetallaallene skeletons are not linear but significantly bent, similarly to the corresponding trisilaallene 2. In contrast to 2, no dynamic disorder was observed for 3 and 4.
Addition of Stable Nitroxide Radical to Stable Divalent Compounds of Heavier Group 14 Elements
作者:Takeaki Iwamoto、Hidenori Masuda、Shintaro Ishida、Chizuko Kabuto、Mitsuo Kira
DOI:10.1021/ja0356784
日期:2003.8.1
The reactions of stable cyclic dialkylgermylene 2 and dialkylstannylene 3 with 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) radical (2 equiv) gave the corresponding 1:2 adducts 4 and 5, respectively, which were characterized by NMR, MS, and X-ray analyses. The kinetics of the stepwise addition of two TEMPO molecules to germylene 2 revealed that the initial addition of TEMPO to 2 was 1010 times slower
稳定的环状二烷基二亚甲基亚甲基2和二烷基亚锡基3与2,2,6,6-四甲基哌啶基-1-氧基(TEMPO)自由基(2当量)反应分别得到相应的1:2加合物4和5,通过NMR表征、MS 和 X 射线分析。将两个 TEMPO 分子逐步添加到锗烯 2 的动力学表明,TEMPO 初始添加到 2 比第二次 TEMPO 添加到所得锗基自由基慢 1010 倍。在定性扰动理论的基础上讨论了速率差异的起源。与 2 和 3 的反应相反,二烷基亚甲硅烷基 1 与 TEMPO 的反应产生了有趣的 1,3-二氧二硅烷衍生物。
Unusual Bonding in Trisilaallene and Related Heavy Allenes
element congeners of allene (heavy allenes) [R(2)M=M'=MR(2); M = M' = Si (1a), M = Si, M' = Ge (1b), M = Ge, M' = Si (1c), and M = M' = Ge (1d)] are comparatively discussed. Using DFT calculations and PMO theory, the origin of the bent and fluxional skeleton of the heavy allenes is ascribed to the Jahn-Tellerdistortion associated with the effective pi-sigma* mixing (pi-sigma* distortion). This type of distortion
丙二烯(重丙二烯)[R(2)M=M'=MR(2); 重14族元素同系物之间的合成、X射线和光谱分析以及不寻常的键合和结构;M = M' = Si (1a), M = Si, M' = Ge (1b), M = Ge, M' = Si (1c), and M = M' = Ge (1d)] 进行了比较讨论。使用 DFT 计算和 PMO 理论,重丙二烯的弯曲和流动骨架的起源归因于与有效 pi-sigma* 混合(pi-sigma* 失真)相关的 Jahn-Teller 失真。这种类型的扭曲被认为是定性描述重主族元素的不饱和化合物的不寻常键合的关键概念。
Reactions of an Isolable Dialkylgermylene with Acyl Chlorides Forming Acyl(chloro)germanes and Diacylgermanes
作者:Huaiyuan Zhu、Ningka Wei、Zhifang Li、Qian Yang、Xu-Qiong Xiao、Guoqiao Lai、Mitsuo Kira
DOI:10.1021/acs.organomet.9b00052
日期:2019.5.13
The reactions of isolable dialkylgermylene 1 with benzoyl and substituted benzoyl chlorides afford the corresponding aroyl(chloro)germanes in high yields. While 2,2-dimethylpropanoyl chloride reacts similarly, the reactions of more reactive alkanoyl chlorides such as acetyl, propanoyl, and butanoyl chlorides give rather unexpectedly the corresponding dialkanoylgermanes 3 together with alkanoyl(chloro)germanes
Unusual reactions of isolable dialkylgermylene and -stannylene with galvinoxyl radical
作者:H. Masuda、T. Iwamoto、C. Kabuto、M. Kira
DOI:10.1023/b:rucb.0000041307.58649.9b
日期:2004.5
The reactions of isolable dialkylgermylene and -stannylene with a galvinoxyl radical were found to give rather unusual cyclic compounds in high yields via intermediate adduct radicals. The structures of the cyclic compounds were determined by X-ray crystallography. We propose a concerted cyclization mechanism in which the abstraction of a hydrogen atom from the tert-butyl group by the galvinoxyl radical is accompanied by the simultaneous attack of the germyl radical center to the tert-butyl carbon atom.