- The Scope of Direct Alkylation of Gold Surface with Solutions of C1-C4 n-Alkylstannanes
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Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms.
- Kaletová, Eva,Kohutová, Anna,Hajduch, Jan,Kaleta, Ji?í,Bastl, Zdeněk,Pospí?il, Lubomír,Stibor, Ivan,Magnera, Thomas F.,Michl, Josef
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p. 12086 - 12099
(2015/10/05)
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- Wurtz-type reductive coupling reaction of primary alkyl iodides and haloorganotins in cosolvent/H2O(NH4Cl)/Zn media as a route to mixed alkylstannanes and hexaalkyldistannanes
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Mixed tetra-alkylstannanes R3SnR′ (R = Et, n-Pr, n-Bu and R′= Me, Et, n-Pr, n-Bu, n-Pent) and R2SnR′2 (R = n-Bu and R′ = Me, Et, n-Pr, n-Bu) can be easily prepared in a one-pot synthesis via coupling reaction of alkyl iodides R′I with R3SnX (X = Cl, I) and R2SnCl2 compounds in cosolvent-H2O(NH4Cl) medium mediated by zinc dust. Coupling also occurs with (Bu3Sn)2O. It has been verified that reactions are possible only with primary alkyl iodides; with secondary alkyl iodides the coupling reaction fails. When alkyl chlorides and bromides are used ditin compounds are obtained instead of the unsymmetrical tetra-alkylstannanes. This represents a route to hexaalkyldistannanes.
- Marton, Daniele,Tari, Massimo
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- CATHODIC SYNTHESIS OF TETRAALKYLTIN COMPOUNDS.
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Methyl bromide and allyl bromide are efficiently reduced at a tin electrode to form tetramethyl and tetraallyl tin. A variety of other bromides with appreciably more negative reduction potentials also produce tetra-substituted tin compounds but the yields are lower. At higher potentials, cathode disintegration is a consequence of the competitive reduction of the carrier electrolyte (Et//4N** plus Br**-).
- Ulery
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p. 1474 - 1478
(2008/10/08)
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