18476-73-8Relevant academic research and scientific papers
Direct Detection, Dimerization, and Chemical Trapping of Dimethyl- and Diphenylstannylene from Photolysis of Stannacyclopent-3-enes in Solution
Duffy, Ian R.,Leigh, William J.
, p. 5029 - 5044 (2015/11/09)
Dimethyl- and diphenylstannylene (SnMe2 and SnPh2, respectively) have been successfully detected and characterized in solution. The stannylenes were generated by photolysis of 1,1,3-trimethyl-4-phenyl- (2) and 3,4-dimethyl-1,1-diphenylstannacyclopent-3-ene (3), respectively, which have been shown to extrude the species cleanly and in high (0.6 2SnCl2) as the stannylene substrate. Laser flash photolysis of 2 and 3 in deoxygenated hexanes affords promptly formed transient absorptions assigned to SnMe2 (λmax = 500 nm; ε500 = 1800 ± 600 M-1 cm-1) and SnPh2 (λmax = 290, 505 nm; ε500 = 2500 ± 600 M-1 cm-1), respectively, which decay with absolute second-order rate constants within a factor of 2 of the diffusional limit in both cases. The decay of the stannylenes is accompanied by the growth of new transient absorptions ascribable to the corresponding dimers, the structures of which are assigned with the aid of DFT and time-dependent (TD) DFT calculations at the (TD)ωB97XD/6-31+G(d,p)C,H,O-LANL2DZdpSn level of theory. Dimerization of SnMe2 affords a species exhibiting λmax = 465 nm, which is assigned to the expected Sn=Sn doubly bonded dimer, tetramethyldistannene (Me2Sn=SnMe2, 16a), in agreement with earlier work. In contrast, the spectrum of the dimer formed from SnPh2 exhibits strong absorptions in the 280-380 nm range and a very weak absorption at 650 nm, on the basis of which it is assigned to phenyl(triphenylstannyl)stannylene (17b). The calculations suggest that 17b is formed via ultrafast rearrangement of a novel phenyl-bridged stannylidenestannylene intermediate (20), which can be formed either directly by "endo" dimerization of SnPh2 or by isomerization of the "exo" dimer, tetraphenyldistannene (16b); the predicted barriers for these rearrangements are consistent with the experimental finding that the observed product is formed at close to the diffusion-controlled rate. Absolute rate and equilibrium constants are reported for the reactions of SnMe2 and SnPh2 with Me2SnCl2 and methanol (MeOH), respectively, in hexanes at 25 °C.
A glimpse at the chemistry of GeH2 in solution. Direct detection of an intramolecular germylene-alkene π-complex
Billone, Paul S.,Beleznay, Katie,Harrington, Cameron R.,Huck, Lawrence A.,Leigh, William J.
scheme or table, p. 10523 - 10534 (2011/09/14)
The photochemistry of 3-methyl-4-phenyl-1-germacyclopent-3-ene (4) and a deuterium-labeled derivative (4-d2) has been studied in solution by steady state and laser flash photolysis methods, with the goal of detecting the parent germylene (GeHs
One-pot formation of allylic chlorides from carbonyl derivatives
Fuchter, Matthew J.,Levy, Jean-Noel
supporting information; experimental part, p. 4919 - 4922 (2009/05/31)
(Chemical Equation Presented) An efficient, one-pot method for the conversion of carbonyl electrophiles to allylic chlorides has been developed, by activating magnesium alkoxides in situ using TiCl4.
Palladium-Catalyzed Three-Component Synthesis of Functionalized Allylamines by Intermolecular Tandem Carbopalladation-Amination
Van Laren, Martijn W.,Diederen, Jeroen J. H.,Elsevier, Cornelis J.
, p. 255 - 259 (2007/10/03)
Highly regio- and stereoselective formation of allylamines has been achieved through a three-component reaction between iodobenzene, an allene, and an amine in acetonitrile, catalyzed by in situ formed and by isolated palladium-diphosphine catalysts.
Preparation of 2-iodo-1,3-butadienes from 1-trimethylsilyl-2,3- butadienes and their functionalizations
Nishiyama, Takashi,Esumi, Tomoyuki,Iwabuchi, Yoshiharu,Irie, Hiroshi,Hatakeyama, Susumi
, p. 43 - 46 (2007/10/03)
Successive treatment of 1-trimethylsilyl-2.3-butadienes with iodine and tetra-n-butylammonium fluoride in the same flask affords 2-iodo-1.3- butadienes in good yields and their palladium-catalyzed carbonylation and alkynylation allows introduction of este
Organomolydenum and Organotungsten Reagents, II. - On the Carbonyl-Olefinating μ-Methylene Complex from Mo2Cl10 and four Equivalents of Methyllithium
Kauffmann, Thomas,Fiegenbaum, Petra,Papenberg, Michael,Wieschollek, Raphael,Sander, Joerg
, p. 143 - 148 (2007/10/02)
Mo2Cl10 reacts at -70 deg C with 4 equivalents of methyllithium to give a methylated thermolabile molybdenum complex.At higher temperatures it forms a thermolabile carbonyl-olefinating reagent which according to NMR data is the μ-CH2 complex Cl3Mo(μ-CH2)2MoCl3 (2).Reactions of 2 with aldehydes, ketones, azomethines, and epoxides are described.Key Words: Carbonyl olefination / μ-Methylene complexes / Molybdenum complexes
The Direct Formation of Functionalized Alkyl(aryl)zinc Halides by Oxidative Addition of Highly Reactive Zinc with Organic Halides and Their Reactions with Acid Chlorides, α,β-Unsaturated Ketones, and Allylic, Aryl, and Vinyl Halides
Zhu, Lishan,Wehmeyer, Richard M.,Rieke, Reuben D.
, p. 1445 - 1453 (2007/10/02)
Highly reactive zinc, prepared by the lithium naphthalenide reduction of ZnCl2, readily undergoes oxidative addition to alkyl, aryl, and vinyl halides under mild conditions to generate the corresponding organozinc compounds in excellent yields.Significantly, the reaction will tolerate a spectrum of functional groups on the organic halides.Accordingly, this approach can now be used to prepare a wide variety of highly functionalized organozinc compounds.In the presence of Cu(I) salts, the organozinc compounds cross-couple with acid chlorides, conjugatively add to α,β-unsaturated ketones, and regioselectively undergo SN2' substitution reactions with allylic halides.They also cross-couple with aryl or vinyl halides with Pd(0) catalysts.
Photolysis of Organopolysilanes. Photochemical Behavior of Phenylethynyldisilanes
Ishikawa, Mitsuo,Sugisawa, Hiroshi,Fuchikami, Takamasa,Kumada, Makoto,Yamabe, Tokio,et al.
, p. 2872 - 2878 (2007/10/02)
The photolysis of phenylethynylpentamethyldisilane (1) afforded 1,1-dimethyl-2-phenyl-3-trimethylsilyl-1-silacyclopropene (8) and 1,1-dimethyl-3-phenyl-3-trimethylsilyl-1-silapropadiene.The absorption and emission spectra of 1 were measured at 300 and 77
