The new aryldihydrogermyllithium complexes RH2GeLi (R = Ph, Mes) are prepared, in good yields, by metallation of the parent trihydrogermane with t-butyllithium in THF. They are characterized by alkylation reactions with MeI. Some germylation reactions are reported: they lead to the formation of new functional aryldihydrogermanes and aryldigermanes by a nucleophilic substitution. These aryldihydrogermyllithium complexes react also with acyl chlorides RCOCl (R = Ph, Mes) to give new diacyl- and triacyl-germanes. These easily add to the carbonyl group of aromatic aldehydes, thereby giving the corresponding alpha-germyl alcohols.
Synthese de composes a liaison MIVBmercure. Precurseurs d'especes monovalentes (germynes), et bivalentes (germylenes), de radicaux centrometalles et d'intermediaires
作者:P. Riviere、A. Castel、J. Satge
DOI:10.1016/s0022-328x(00)85661-2
日期:1981.6
Polynuclear germylmercury compounds are obtained from the reaction of organohydrogermanes PhnGeH4−n or digermanes Ph2nGe2H4−n (n = 1, 2) with dialkylmercury R2Hg. Di- or tri-mercurated geminal polygermates thus synthesized generally present a low stability and undergo thermal- or photo-decompositions leading to the corresponding monovalent (germynes), divalent (germylenes) or, trivalent (germanium
多有机环锗烷基汞化合物是从有机氢锗酸Ph n GeH 4- n或二锗烷基Ph 2 n Ge 2 H 4- n(n = 1,2)与二烷基汞R 2 Hg的反应中获得的。如此合成的二或三聚汞的双聚锗酸酯通常表现出较低的稳定性,并且会发生热分解或光分解,从而导致相应的单价(锗烷),二价(亚锗烷)或三价(锗中心自由基)物种以及中间双自由基可以认为是锗双键化合物的极限形式。这样的中间体已经在化学和光谱学上表征。
Synthesis and reactivity of germyliron complexes [Ph2HGeFe(η5-C5H5)(CO)2] and [RH2GeFe(η5-C5H5)(CO)2] (R = Ph or 2,4,6-Me3C6H2)
The new complexes [Ph2HGeFe(η5-C5H5)(CO)2] (1) and [RH2GeFe(η5-C5H5)(CO)2] (R = Ph or Mes, 2a or 2b) were prepared by a substitution reaction, from the corresponding arylhalohydrogermanes and the iron salt. Their characterization by IR, 1H and 13C NMR and mass spectroscopy is reported. They are easily transformed into the mono- or di-halogermyl compounds by action of N-chlorosuccinimide. Treatment
新的配合物[PH 2 HGeFe(η 5 -C 5 H ^ 5)(CO)2 ](1)和[RH 2 GeFe(η 5 -C 5 H ^ 5)(CO)2 ](R = PH或MES,通过取代反应由相应的芳基卤代氢锗烷和铁盐制备2a或2b)。据报道,它们通过IR,1 H和13 C NMR和质谱表征。在N-氯代琥珀酰亚胺的作用下,它们很容易转变为单或二卤代戊基化合物。治疗1用锂试剂(LDA或t BuLi)处理会导致环戊二烯基环发生初始去质子化,并伴随着胚芽基的迁移。中间铁盐通过将MeI猝灭产生MeFe(η 5 -C 5 H ^ 4 GeHPh 2)(CO)2。在氯铂酸的存在下,与苯乙炔或甲基乙炔基酮进行加氢甲酰化反应,主要生成加合物的α-异构体。
Riviere, Pierre; Riviere-Baudet, Monique; Castel, Annie, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1987, vol. 17, p. 539 - 558
作者:Riviere, Pierre、Riviere-Baudet, Monique、Castel, Annie、Satge, Jacques、Lavabre, Anne
DOI:——
日期:——
PIVIERE P.; CASTEL A.; SATGE J., J. ORGANOMETAL. CHEM., 1981, 212, NO 3, 351-367
作者:PIVIERE P.、 CASTEL A.、 SATGE J.
DOI:——
日期:——
RIVIERE, PIERRE;RIVIERE-BAUDET, MONIQUE;CASTEL, ANNIE;SATGE, JACQUES;LAVA+, SYNTH. AND REACT. INORG. AND METAL-ORG. CHEM., 17,(1987) N 5, 539-557