dimesitylgermanedithiolate reacted with titanocene or zirconocene dichloride to give 2,2-dimesityl-1,3-dithia-2-germa-4-titanacycle (3a) and its zirconocene analogue (3b), which afforded a stable 2,3,4,5-tetrathiagermolane (4) in treatment with S2Cl2. The reaction of 3b with Ph2GeCl2 gave unsymmetric 1,3,2,4-dithiadigermetane (5). The bis(η5-cyclopentadienyl) derivative of cis-2,3-di-t-butyl-2,3-diphenyl-1
Reductive coupling reactions of dihalogenogermanes with magnesium and magnesium bromide: simple preparation of cyclotrigermanes and cyclotetragermanes
作者:Wataru Ando、Takeshi Tsumuraya
DOI:10.1039/c39870001514
日期:——
The reactions of various dihalogenogermanes with Mg and MgBr2 in tetrahydrofuran produce the corresponding cyclotrigermanes and cyclotetragermanes; the ring size of the products depends on the steric bulk of substituents on germanium.
Pentagerma[1.1.1]propellane: A Combined Experimental and Quantum Chemical Study on the Nature of the Interactions between the Bridgehead Atoms
作者:Dominik Nied、Wim Klopper、Frank Breher
DOI:10.1002/anie.200805289
日期:2009.2.9
Ge, whiz! A detailed study of the synthesis, structure, redox chemistry, and bonding properties of pentagerma[1.1.1]propellane (1, see picture) examines fundamental aspects of the interactions between the bridgehead germanium atoms. DFT and CASSCF calculations unravel the biradicaloid characteristics of 1, and preliminary reactivity studies indicate that 1 features some radical‐type behavior.
Dimesitylgermylidene p-toluene sulfonamide: a new stable germanium—nitrogen doubly bonded species
作者:F. El Baz、M. Rivière-Baudet、M. Ahra
DOI:10.1016/s0022-328x(97)00449-x
日期:1997.12
A new stable germanium doubly bondedspecies is obtained by dehydrohalogenation of the corresponding N-halogenogermyl p-toluene sulfonamide. The dimesitylgermylidene p-toluene sulfonamide is a stable and very reactive reagent leading to addition reactions with protic species such as water, t-butanol or chloroform. With 3,5-di-t-butyl ortho-diphenol, the reaction leads to the corresponding dimesitylgermadioxolane
通过相应的N-卤代锗烷基对甲苯磺酰胺的脱卤化氢获得了一种新的稳定的锗双键物种。二烯丙基亚苄基对甲苯磺酰胺是一种稳定且反应性极强的试剂,可导致与质子物种(例如水,叔丁醇或氯仿)的加成反应。与3,5-二-吨-丁基邻二酚,将反应导致与消除相应dimesitylgermadioxolane p -甲苯磺酰胺。与苯甲醛一起,二聚异亚丙基亚磺酰胺导致假维蒂格反应,并形成相应的亚苄基对甲苯磺酰胺。与3,5-二ŧ-叔丁基邻醌,该反应的第一步涉及单电子转移,最终导致二甲基苯乙烯基二氧杂环戊烷,并生成对甲苯磺酰胺基自由基,其特征是复制成N,N-双(对甲苯磺酰基)肼。
Aluminium Functionalized Germanes: Intramolecular Activation of Ge–H Bonds, Formation of a Dihydrogen Bond and Facile Hydrogermylation of Unsaturated Substrates
RR′(H)Ge‐C(AlR′′2)=C(H)‐tBu [4a, R = R′ = Mes, R′′ = tBu; 4b, R = R′ = Mes, R′′ = CH(SiMe3)2; 5a, R = R′′ = tBu, R′ = CH2CH2tBu; 5b, R = tBu, R′ = CH2CH2tBu, R′′ = CH(SiMe3)2], was synthesized by hydroalumination of the respective alkynylgermanes, RR′(H)Ge‐C≡C‐tBu 3, with R′′2Al–H [R′′ = tBu, CH(SiMe3)2]. In the solid state compound 5b showed a contact between Al and the Ge bound H atom (293 pm) which