1066-45-1Relevant articles and documents
Kraus, C. A.,Greer, W. N.
, p. 2629 - 2633 (1922)
Alkyl- and acyl-substituted vinylstannanes: Synthesis and reactivity in electrophilic substitution reactions
Cochran, John C.,Prindle, Vicki,Young, Heather A.,Kumar, Mark H.,Tom, Samson,Petraco, Nicholas D. K.,Mohoro, Clare,Kelley, Brendan
, p. 885 - 902 (2002)
Six substituted vinylstannanes have been prepared. (E)- and (Z)-2-trimethylstannyl-2-butene, (1) and (2), respectively, 2-methyl-1-(trimethylstannyl) propene, (3), and 3-methyl-2-trimethylstannyl-2-butene, (4), were prepared by coupling the appropriate lithium or Grignard reagent with chlorotrimethylstannane. 3-Trimethylstannyl-3-butene-2-one, (5), and (Z)-3-trimethylstannyl-3-hexene-2-one, (6), were prepared by palladium(O) catalyzed hydrostannation of the appropriate ynone. This reaction was regiospecific such that the trimethylstannyl and carbonyl groups were bonded at the same vinyl carbon. The reaction was also stereospecific giving syn addition in each case. However, isomerization to a mixture of isomers was observed for the reaction of (5) with Me3SnD and complete isomerization of E-(6) to Z-(6). Each compound was characterized by 1H, 13C, and 119Sn NMR. The reactivity to protodestannylation was determined for each compound by spectrophotometric measurement of second order rate constants. The reactivity of the multimethyl-substituted vinylstannanes was consistent with the reactivity determined previously for monomethyl-substituted vinylstannanes. However, two methyl groups at the remote vinyl carbon exhibited a synergistic activating effect on the protodestannylation reactivity. The acyl group was found to be deactivating for protodestannylation. The stereochemistry of the reaction was round to take place with retention of configuration.
Synthesis and reactivity of germanium heterocycles containing germanium - tin bonds
Nosov,Lalov,Borovik,Lee,Egorov,Nefedov
, p. 2623 - 2626 (1996)
Previously unknown stannyl-substituted germanium heterocycles, 1,1-bis(trimethylstannyl)-2,3,4,5-tetraphenyl-1-germacyclopenta-2,4-diene and 1,1-bis(trimethylstannyl)-3,4-dimethyl-1-germacyclopent-3-ene were synthesized, and their photolysis and chemical
Tombe, F. J. A. des,Kerk, G. J. van der,Noltes, J. G.
, p. 173 - 180 (1973)
Reagents based on cyclopentadienyl derivatives of the group 14 elements for the synthesis of indium(I) derivatives. Crystal and molecular structure of in(C5H4SiMe3)
Beachley Jr.,Lees,Glassman,Churchill, Melvyn Rowen,Buttrey, Lisa A.
, p. 2488 - 2492 (1990)
Cyclopentadienyl trimethyl derivatives of the group 14 elements (C5H4MMe3, M = Si, Ge, Sn) have been investigated for their effects on indium(I) chemistry. The compounds In(C5H4SiMe3) and In(C5H4GeMe3) have been prepared from the corresponding lithium cyclopentadienyl reagent LiC5H4MMe3 and InCl. Characterization data have included partial elemental analyses (C, H), physical properties, IR and 1H NMR spectroscopic data, oxidation reactions with dilute aqueous HCl, and a single-crystal X-ray structural study in the case of In(C5H4SiMe3). When cyclopentadienyltrimethyltin, C5H5SnMe3, was combined with InCl in diethyl ether, In(C5H5) and Me3SnCl were formed in good yields. In(C5H4SiMe3) crystallizes in the centrosymmetric monoclinic space group P21/c (C2h5; No. 14) with a = 9.171 (5) ?, b = 9.910 (6) ?, c = 11.677 (7) ?, β = 97.30 (5)°, V = 1052.6 (11) ?3, and Z = 4. Diffraction data (Mo Kα radiation, 2θ = 4.5-50.0°) were collected on a Syntex P21 automated four-circle diffractometer, and the structure was solved and refined to RF = 5.0% and RwF = 4.0% for all 1851 independent reflections (RF = 3.1% and RwF = 3.5% for those 1336 data with |Fo| > 6σ|Fo|)). The solid-state structure consists of infinite zigzag chains of [In(C5H4SiMe3)]∞. Each indium atom interacts with two η5-C5H4SiMe3 ligands with a centroid?In?centroid angle of 131.78°, and each η5-C5H4SiMe3 ligand is linked to two indium atoms with In?centroid?In angles of 175.94°. There are no short interstrand In?In interactions, the shortest such distance being 5.428 ?. Thus, In(C5H4SiMe3) is the first cyclopentadienylindium(I) derivative with no apparent indium-indium interactions.
Homolytic Substitution at Carbon: 1,3- and 1,5-Ring Closures in Organotin-Substituted Radicals
Davis, Dennis D.,Ahmed, Fahim U.
, p. 7653 - 7654 (1981)
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Abel et al.
, p. 260,261 (1966)
Berghe, E. V. van den,Kelen, G. P. van der
, p. 522 - 527 (1966)
Investigation of the catalyst system tungsten hexachloride/tetramethyltin; reduction of tungsten hexachloride during the alkylation step
Thorn-Csanyi, E.,Kessler, M.
, p. 253 - 260 (1991)
The alkylation steps in the catalyst system tungsten hexachloride/tetramethyltin have been studied kinetically. FTIR examinations in combination with UV and GC results have shown that the alkylation of tungsten hexachloride is accompanied by a reduction of the tungsten component. Ether addition increases the amount of the tungsten chloride which is reduced.
Kato, S.,Kato, T.,Mizuta, M.,Itoh, K.,Ishii, Y.
, p. 167 - 171 (1973)
Eaborn, C.,Najam, A. A.,Walton, D. R. M.
, (1972)
Ssebuwufu, P. John,Glockling, F.,Harriott, P.
, p. L35 - L38 (1985)
Cardin et al.
, p. C70 (1973)
Kozuka,Naribayashi
, p. 3638 (1979)
Simple procedure for conversion of a trialkyltin fluoride into the corresponding chloride or bromide
Mitchell, Terence N.,Kwetkat, Klaus,Godry, Bernd
, p. 1633 - 1634 (1991)
Trialkyltin fluorides are converted into the chlorides or bromides on treatment with an excess of the corresponding sodium halide in tetrahydrofuran.
Armbrecht,jun. et al.
, p. 3218 (1969)
Redox properties of dihalogermylenes, dihalostannylenes and their complexes with Lewis bases
Lee, V.Ya.,Basova, A.A.,Matchkarovskaya, I.A.,Faustov, V.I.,Egorov, M.P.,et al.
, p. 27 - 34 (1995)
Reduction and oxidation potentials of Gel2, GeBr2 * B (B = dioxane, PPh3), GeCl2 * B (B = dioxane, PPh3, AsPh3, Py, dip), SnCl2 * dioxane, SnX2 (X = F, Cl Br, I) were measured in MeCN at 20 deg C.The data obtained indicate that in many cases the EX2 and EX2 * B (E = Ge, Sn) can act not only as a good reducing agents, but also as strong oxidants.Examples of redox reactions in which EX2 and EX2 * B react as oxidizing agents were found.The variation of the redox potentials of the dihalogermylenes and dihalostannylenes with complexation and with the nature of the halogen substituent and the Lewis base is discussed.In some cases (GeI2, GeX2 * B; X = Cl, Br, B = dioxane, PPh3), the reduction or oxidation was found to be quasi-reversible, indicating the presence of relatively stable ion radicals.AM1 calculations on GeCl2 * dioxane and GeCl2 * PH3 complexes show that the complexation destabilizes both the highest occupied and the lowest unoccupied MOs of the carbene analogues.The complexation reduces the IP and lowers the oxidation potential; its intluence on the electron affinity is not straightforward.Calculations of the ion radicals of GeCl2 and GeCl2 * B (B = dioxane, PH3 ) show that in the ground state an unpaired electron occupies ?-MO in the cation and ?-MO in anion radicals.Keywords: Germanium; Tin; Germylenes; Stannylene; Electrochemistry; AM1 calculations
Conversion of Alkyltantalum Chlorides to Fluorides Using Trimethyltin Fluoride as a Fluorinating Agent. Crystal Structures of (p-MeC6H4CH2)3TaF2, (Me3SnCl.Me3SnF.TaF5)n, (Me3Si)2CHTaCl4
Guzyr, Olexandr I.,Schormann, Mark,Schimkowiak, Jürgen,Roesky, Herbert W.,Lehmann, Christopher,Walawalkar, Mrinalini G.,Murugavel, Ramaswarny,Schmidt, Hans-Georg,Noltemeyer, Mathias
, p. 832 - 836 (1999)
The reactions of alkyltantalum chlorides with trimethyltin fluoride were found to be highly dependent on the number of organic ligands on tantalum as well as on the electronic and the steric nature of the substituants. The synthesis of trialkyltantalum difluorides of general formula (RCH2)3TaF2 (R = Ph, 1; R = p-Tol, 2; R = Me3Si, 3) and the first example of the alkyltantalum tetrafluoride (Me3Si)2CHTaF4 (8) are reported. The compounds (p-MeC6H4-CH2)3TaF2, (Me2SnCl.Me3SnFTaF5)n (Me3Si)2CHTaCl4, {(Me3Si)2CHTaCl4(Me3Si) 2CH]2Ta2-Cl6μ2-O)}, and (Me3Si)2CHTaF4 respectively have been characterized by single-crystal X-ray structural analysis.
STUDY OF THE REDISTRIBUTION REACTION OF TETRAMETHYLTIN WITH DIMETHYLTIN DICHLORIDE IN SEVERAL APROTIC SOLVENTS.
Yamashita,Saito,Yoshino,Takahashi
, p. 2555 - 2558 (1983)
The redistribution reaction of tetramethyltin with dimethyltin dichloride was studied in eight aprotic solvents by using the **1H NMR technique. The second-order rate constant of the reaction (ln k//2) is proportional to the dielectric constant of the solvent. There is a weak relation between the rate constants (ln k//2) and the values of **2J(Sn-H) of Me//2SnCl//2 in several solvents, which are considered to be related to the coordination ability of the solvents. The rate constants are also related to Kosower's Z values of the solvents. The activation entropies of the reaction in four typical solvents have large negative values. This predicts that the reaction proceeds via a four-center transition state.
MECHANISM OF THE REACTION OF (ARYLOXY)TRIMETHYLSTANNANE WITH METHANESULFONYL CHLORIDE - SOLVENT AND SUBSTITUENT EFFECTS ON THE RATE OF THE REACTION.
Kozuka,Yamaguchi,Tagaki
, p. 573 - 576 (1983)
A kinetic study has been conducted on the reactions of (aryloxy)trimethylstannanes with methanesulfonyl chloride giving chlorotrimethylstannane and aryl methanesulfonates. The reaction was found to obey a second order kinetic equation. The solvent effect on the rate of the reaction appeared obscure although a small rate enhancement was observed in a polar solvent. Substituent effect of the aryloxyl group was found to be dependent on the solvent used while a clear isokinetic relationship was observed. A charge separated four-center transition state has been suggested for the reaction.
Jean,Guillerm,Lequan
, p. P1-P2 (1970)
Platinum-catalyzed phenyl and methyl group transfer from tin to iridium: Evidence for an autocatalytic reaction pathway with an unusual preference for methyl transfer
Smith, Stuart E.,Sasaki, Jennifer M.,Bergman, Robert G.,Mondloch, Joseph E.,Finke, Richard G.
, p. 1839 - 1841 (2008)
Platinum complexes have been found to catalyze the transfer of σ-bound ligands to the Ir center in Cp*(PMe3)IrCl2 (Cp* = η5-C5Me5) from Bu3SnPh and PhxSnMe
Roberts, R. M. G.
, p. 323 - 330 (1971)
A utility for organoleads: Selective alkyl and aryl group transfer to tin
Arias-Ugarte, Renzo N.,Pannell, Keith H.
, p. 1703 - 1708 (2018/02/09)
Me4Pb and Ph4Pb readily transfer methyl or phenyl groups to an equivalent molar ratio of tin(iv) chlorides in the order SnCl4 > MeSnCl3 > Me2SnCl2 > Me3SnCl, often in a selective manner. Me3PbCl and Ph3PbCl specifically transfer a single methyl/phenyl group under the same reaction conditions to produce recovered yields in >75%. Specific transfer of 2 methyl groups from PbMe4 can be achieved at elevated temperatures and/or a 2:1 molar ratio Pb:Sn.
Mechanism and Unusual Fragmentation Selectivities of Aryltrialkylstannane Cation Radicals
Luo, Pu,Dinnocenzo, Joseph P.
, p. 9240 - 9246 (2015/09/28)
Aryltrialkylstannane cation radicals were generated and characterized by nanosecond transient absorption spectroscopy. Kinetics show the fragmentations of the stannane cation radicals occur by a bimolecular, nucleophile-assisted mechanism (SN2). Consistent with this hypothesis, steric effects on both the nucleophile and the stannane cation radicals were observed. Steady-state, preparative photooxidation experiments show that aryltrimethylstannane cation radicals have an unusual preference for loss of aryl radicals over methyl radicals and that the selectivity for aryl vs methyl radical loss is dependent on the identity of the nucleophile. The preference for loss of aryl radicals is rationalized by a hypothesis based on Bents rules.
