Reactivity, absorption and emission of dimethylgermylene photo-generated from dodecamethylcyclohexagermane
摘要:
The UV photolysis of dodecamethylcyclohexagermane (1) in cyclohexane at room temperature proceeds readily with loss of dimethylgermylene species to give two of the lower homologs, decamethylcyclopentagermane (2) and octamethylcyclotetragermane (3). The photochemically generated dimethylgermylene species reacts with 2,3-dimethylbuta-1,3-diene or CCl4 to give 1,1,3,4-tetramethyl-1-germacyclopent-3-ene or trichloromethyldimethylchlorogermane, respectively. The transient absorption of 1 in cyclohexane at 450 nm obtained by laser flash-photolysis is due to dimethylgermylene. The reaction rates of dimethylgermylene with some substances are examined. In 3-methylpentane glass dimethylgermylene shows an absorption band at 430 nm and a fluorescence peak at 650 nm. The photo-generated germylene appears to be the singlet ground state.
six-membered cyclic oligogermanes, such as dodecamethylcyclohexagermane, (Me2Ge)6, reacted with alkynes in the presence of platinum catalysts to yield 1,4-digermacyclohexa-2,5-dienes in ca. 30% yield. The reactions of phenylacetylene with 1,2-digermacyclohexa-3,5-dienes afforded the corresponding 1,4-digermacycloocta-2,5,7-trienes in 93% yield. Bis(germyl)platinum complexes having various tertiary phosphine
Some new germanium analogues of 1,3-cyclohexadiene, 3,4,5,6-tetraphenyl-, 3,6-diphenyl-, and 3,4,5,6-tetramethyl-1,2-digermacyclohexa-3,5-diene and 3,4,5,6-tetraphenyl-1-germa-2-silacyclohexa-3,5-diene, were prepared and fully characterized by spectroscopic methods. On photolysis, the 1,2-digermacyclohexa-3,5-diene underwent extrusion of dialkylgermylene (R2Ge:) to give the corresponding germacyclopentadiene
1,3-环己二烯,3,4,5,6-四苯基-,3,6-二苯基-和3,4,5,6-四甲基-1,2-二甲基环己-3,5-的一些新的锗类似物制备了二烯和3,4,5,6-四苯基-1-锗-2-硅环六-6-3,5-二烯,并通过光谱法对其进行了全面表征。在光解中,将1,2-二硬脂基环己-3,5-二烯进行二烷基亚锗烯(R 2 Ge :)的挤出,以得到相应的生殖环戊二烯。在辐射下,1-germa-2-silacyclohexa-3,5-diene通过挤出R 2 Ge:优先产生了silacyclopentadiene 。讨论了这些光解的机理。
Laser Flash Photolysis Studies of Some Dimethylgermylene Precursors
作者:Farahnaz Lollmahomed、William J. Leigh
DOI:10.1021/om9000814
日期:2009.6.8
The laserflashphotolysis of dodecamethylcyclohexagermane (1) and dimethylphenyl(trimethylsilyl)germane (5), two known photochemical precursors to dimethylgermylene (GeMe2), has been reinvestigated. Laserflashphotolysis of 1 in hexane solution affords markedly different results than were reported in an earlier study of this compound in cyclohexane. The present study shows it to yield two primary
Molecular Beam Photochemistry of Organopolysilanes and Organopolygermanes
作者:Ian Borthwick、Lawrence C. Baldwin、Mark Sulkes、Mark J. Fink
DOI:10.1021/om990880u
日期:2000.1.1
cyclic precursors (Me2Si)6 and 1,3-diphenyl-1,2,2,3-tetramethyl-1,2,3-trisilacycloheptane. Likewise, dimethylgermylene (Me2Ge:) was directly observed in the photolysis of (Me2Ge)6. One-photon photolysis of the noncyclic polysilanes PhMeSi(SiMe3)2 and PhSi(SiMe3)3, however, gave radical products derived from the homolytic scission of a single Si−Si bond with little or no evidence of silylene being generated
Discrete palladium clusters that consist of two mutually bisecting perpendicular planes
作者:Naoya Kojima、Misaki Kato、Yusuke Sunada
DOI:10.1039/d2sc02302d
日期:——
The construction of Pd7Sn4 and Pd8Ge6 clusters that consist of two mutually bisecting perpendicular planes was accomplished by the reaction of [Pd(CNtBu)2]3 with Me3Sn–SnMe2–SnMe3 or Ge6Me12.