- Organometallic iridium complexes of (Z)-1-Phenyl-2-(4′,4′-dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ate: Structural aspects, reactivity and applications in the catalytic dehydrogenation of Alkanes#
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The treatment of [IrCl(cod)]2 with (Z)-1-phenyl-2-(4′,4′- dimethyl-2′-oxazolin-2′-yl)-eth-1-en-1-ol (HL) in the presence of base yields the first Ir complex of this ligand class: Ir(κ2- N,O-L)(cod) (3). Complex 3 is reactive with MeI or HSnPh3 to yield the oxidative addition products 4 (trans-Ir(Me)I(κ2-N,OL)( cod)) and 5 (cis-IrH(SnPh3)(κ2-N,O-L)(cod)), respectively. All three of these derivatives have been fully characterised including via single crystal X-ray diffraction data. Complex 3 is generally resistant to cod ligand substitution but shown to be reactive with CO (g) to give Ir(κ2-N,O-L)(CO)2 (6). In addition, 3 is demonstrated to be a dehydrogenation catalyst for the conversion of C8H16 into cyclooctene and H2 under acceptorfree conditions.
- Clément, Roxanne,Gossage, Robert A.,Lough, Alan J.,May, Kathleen L.
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supporting information
p. 2042 - 2047
(2021/09/16)
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- Novel amino propyl substituted organo tin compounds
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In this work, a new synthetic pathway yielding unprotected amino propyl tin compounds is described.For this purpose, mono stannanes with different substitution patterns are used.In a first step, tin hydrides are deprotonated using lithium diisopropyl amide and mixed with an electrophile containing a protected amine in the cω;-position.After deprotection via acidic hydrolysis, the desired amino propyl tin compounds are obtained in high yield and purity.The thermal reaction behavior of the amino propyl tin hydrohalide intermediates containing one aromatic residue at the central tin atom is also investigated.For this purpose, amino propyl tin hydrohalides are heated under vacuum until the aromatic hydrocarbon is liberated.This thermal treatment leads to so far unknown tin halides containing an amino propyl side chain.For all of these substances detailed liquid 1H, 13C, and 119Sn-nuclear magnetic resonance (NMR) data were obtained, and in one case solid state NMR is also conducted.Regarding solids, single crystal X-ray analysis is performed.Some derivatization reactions with these new substances are demonstrated, especially the synthesis of an amino propyl tin carboxylate, which might be very interesting for biological, pharmaceutical, or technical processes.
- Pichler, Johann,Torvisco, Ana,Bottke, Patrick,Wilkening, Martin,Uhlig, Frank
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p. 565 - 573
(2014/06/10)
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- Stereoselective radical tandem cyclohydrostannation of optically active di-unsaturated esters of TADDOL
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This paper reports the results obtained in a study on the radical addition of triorganotin hydrides, R3SnH (R = Me, n-Bu, Ph; Neophyl), to four TADDOL unsaturated diesters. It was found that diese reactions lead in high yields to products of cyclohydrostannation. It was also found that whereas the addition of these hydrides to TADDOL diacrylate and TADDOL dimethacrylate leads to the expected mixtures of two and four cycloundecane diastereoisomers, respectively, the addition of triphenyltin hydride to TADDOL disubstituted acrylates yields only four out of the 16 possible stereoisomers. The observed high stereoselectivity is consistent with the radical tandem cyclohydrostannation mechanism proposed. Only in the case of the hydrostannation of TADDOL diacrylate with trimethyl- and triphenyltin hydrides could the diastereoisomers obtained in higher proportion (5a and 8a) be isolated in pure form. The subsequent reduction (lithium aluminum hydride) of macrolides 5a and 8a afforded the corresponding optically active diols 26 and 27 in high yield. Full 1H, 13C, and 119Sn NMR data are given.
- Gerbino, Dario C.,Koll, Liliana C.,Mandolesi, Sandra D.,Podesta, Julio C.
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p. 660 - 665
(2009/01/30)
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- Efficient syntheses of four stable-isotope labeled (1R)-menthyl (1S,2S)-(+)-2-phenylcyclopropanecarboxylates
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Many carbenoid cyclopropanation reactions promoted by chiral catalysts give product mixtures reflecting impressive diastereo- and enantioselectivities. Few provide a single chiral product efficiently. This limitation has been overcome in cyclopropanations of styrene and isotopically labeled styrenes with α-diazoacetates. Convenient syntheses on a 20 g scale of each of four chiral isotopically labeled (1R)-menthyl (1S,2S)-2- phenylcyclopropanecarboxylates (the 1-d-3-13C, 1,(3S)-d2, 1,2,(3S)-d3, and 1,3,3-d3 isotopomers) of better than 99% ee have been realized. The Royal Society of Chemistry 2006.
- Keliher, Edmund J.,Burrell, Richard C.,Chobanian, Harry R.,Conkrite, Karina L.,Shukla, Rajesh,Baldwin, John E.
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p. 2777 - 2784
(2008/09/16)
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- Formation of cyclo- and polystannanes by dehydrogenative stannane coupling catalyzed by platinum(II) complexes
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Reaction of (PhMe2P)2PtMe2 or [(κ2-P,N)-Ph2PC2H4NMe 2]PtMe2 with an excess of H2SnBu2 or H2SnPh2 resulted in the
- Thompson, Susan M.,Schubert, Ulrich
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p. 1959 - 1964
(2008/10/09)
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- Synthesis, characterization, and reactivity of triphenylsilyl, triphenylgermyl, and triphenylstannyl derivatives of zirconium and hafnium
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The crystalline lithium silyl compound (THF)3LiSiPh3 (1) was isolated from the reaction of Ph3SiSiPh3 with lithium in tetrahydrofuran. This compound and tetrahydrofuran solutions of LiEPh3 (E = Ge, Sn
- Woo, Hee-Gweon,Freeman, William P.,Don Tilley
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p. 2198 - 2205
(2008/10/08)
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- Cyclic ketones and their use as perfuming ingredients
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Novel compounds of formula STR1 wherein the dotted lines indicate the location of a single or double bond, symbol R1 stands for a hydrogen atom or a methyl radical, symbol R2 represents a linear or branched, saturated or unsaturated, C1 to C4 alkyl radical, provided that R1 is not hydrogen when R2 represents a methyl or n-propyl radical and the ring is saturated. Compounds (Ia) are useful as perfuming ingredients. A process for their preparation is disclosed.
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- Tin steroids and their uses
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Tin steroids and methods of using the same. The tin steroid compounds are prepared by the reaction of various organotin compounds with various steroids. Said compounds inhibit the growth of malignant tumors. They are also useful as insecticides, larvicides, bactericides and fungicides.
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- Tin steroids and their use as antineoplastic agents
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A method and composition for the preparation of steroid compounds by the reaction of various organotin compounds with steroids. Said compounds retard the growth of malignant tumors and, in some cases, completely destroy the tumor.
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- THE REACTIONS OF DIBORANE WITH ARYL-ORGANOTIN COMPOUNDS
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A number of tetraaryltin compounds, Ar4Sn (where Ar = phenyl, o- and p-tolyl, and p-chlorophenyl) and tryphenyltin compounds, PH3SnX (where X = Cl, H, OH, OCOCH3 and OCOCF3) have been treated with diborane in tetrahydrofuran.Transmetallation occurs in which one or more aryl groups are transferred to boron.The organoboron intermediates give phenols upon oxidation and boronic and borinic acids upon hydrolysis.Pyridine complexes of organoboranes have also been isolated.
- Pickles, G. M.,Spencer, T.,Thorpe, F. G.,Chopa, A. B.,Podesta, J. C.
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- Metal hydrides as electron donors. The mechanism of oxidative cleavage with tris(phenanthroline) complexes of iron(III)
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The group 4 metal hydrides HMR3 (M = silicon, germanium, tin; R = alkyl, phenyl) react spontaneously with 2 equiv of tris(phenanthroline)iron(III) perchlorate, FeL3(ClO4)3, in acetonitrile solutions. Although the second-order kinetics (first order in each reactant) indicate that the selective cleavage of only the hydrido-metal bond proceeds from a rate-limiting bimolecular process, there is no significant deuterium kinetic isotope effect. The free-energy dependence of the second-order rate constant kH for the silicon and germanium hydrides follows the Marcus relationship with slope α close to the theoretical value of 8.5 for an outer-sphere electron-transfer process. The paramagnetic cation HMR3+, similar to that formed by electron impact or photoionization of HMR3, is postulated to be a metastable intermediate which undergoes spontaneous scission of the hydrogen-metal bond, followed by a further rapid oxidation of the fragment by a second equivalent of FeL33+. The rate-limiting, outer-sphere mechanism for HMR3 accords with that previously established for electron transfer between the related series of peralkylmetals MR4 and the same FeL33+ complexes. The electron-transfer rate constants kH and kR for HMR3 and MR4, respectively, are compared for their sensitivity to changes in the standard reduction potentials E° of FeL33+ and the gas-phase ionization potentials ID of HMR3 and MR4. Polarization and solvation effects appear to be especially important in electron transfer from metal hydrides, especially those of tin.
- Wong,Klingler,Kochi
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p. 423 - 430
(2008/10/08)
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- Organotin chemistry XI. (2-cyanoethyl)tin bromides
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The syntheses of bis(2-cyanoethyl)tin dibromide and (cyanoethyl)-tin tribromide by reaction of bromine with diphenylbis(2-cyanoethyl)tin and triphenyl(2-cyanoethyl)tin, respectively, in an inert solvent are reported. Based on the nitrile absorption bands in nujol, it is concluded that tris(2-cyanoethyl)tin bromide and (2-cyanoethyl)tin tibromide, but not bis(2-cyanoethyl)tin dibromide, are associated in the solid state. The nature of these associations are discussed in detail. Molecular weight determinations show that tris(2-cyanoethyl)tin bromide and bis(2-cyanoethyl)tin dibromide are monomeric in tetrahydrofuran and that (2-cyanoethyl)tin tribromide is monomeric in benzene.
- Reifenberg, Gerald H.,Considine, William J.
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p. 505 - 509
(2008/10/08)
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