- M -C2B10H11HgCl/AgOTf-Catalyzed Reaction for Reductive Deoxygenation
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A m -C2B10H11HgCl/AgOTf-catalyzed reaction of allyl silyl ethers with N -Boc- N ′-tosylhydrazine has been developed. Under mild conditions, the resulting allyl hydrazine products were transformed into naked alkenes in good yield. Furthermore, the used m -C2B10H11HgCl could be recovered quantitatively.
- Yamasaki, Naoto,Kanno, Marina,Sakamoto, Kyohei,Kasai, Yusuke,Imagawa, Hiroshi,Yamamoto, Hirofumi
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supporting information
p. 169 - 175
(2018/03/26)
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- Aryl-Allene Cyclization via a Hg(OTf)2-Catalytic Pathway
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Hg(OTf)2-catalyzed aryl-allene cyclization accompanied by formation of a quaternary carbon center has been realized. Deuterium-labeling experiments and computational modeling were used to propose a novel catalytic pathway involving direct H-transfer from the aromatic ring to the vinyl mercury moiety followed by mercury 1,2-migration.
- Yamamoto, Hirofumi,Ueda, Maho,Yamasaki, Naoto,Fujii, Akiyoshi,Sasaki, Ikuo,Igawa, Kazunobu,Kasai, Yusuke,Imagawa, Hiroshi,Nishizawa, Mugio
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supporting information
p. 2864 - 2867
(2016/07/06)
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- The kinetics and stereochemistry of base hydrolysis of the seven isomers of [Co(dien)(ampy)Cl]2+ and [Co(dien)(ibn)Cl]2+
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The kinetics and stereochemistry for the base catalysed substitution reactions of all seven isomers (4 mer and 3 fac) of both [Co(dien)(ibn)Cl]2+ and [Co(dien)(ampy)Cl]2+ have been studied in detail, for water and azide ion as entering groups. The stereochemistry for the azide ion anation of some of the [Co(dien)(diamine)OH]2+ species have also been investigated. The mer isomers are of comparable reactivity and amongst the fastest reacting pentaaminechlorocobalt(III) complexes known. They are also much faster to hydrolyse than the fac species. In both the ibn and ampy systems, a common product stereochemistry is observed for the four reactant mer isomers (the product is a mixture of all four mer configurations), for both azide ion and water as nucleophiles, but not for the three fac reactants (H2O as nucleophile). The kinetic and equilibrium distributions are quite different. For the mer isomer reactions, a common trigonal bipyramidal five-coordinate intermediate deprotonated at the sec-NH of the dien is overwhelmingly implicated. The substitution mechanisms are argued in detail. Other data reported include isomerisation rates and equilibrium distributions for some mer-hydroxo and a mer-aqua complex of exceptional reactivity, equilibrium distributions for the mer-phosphato complexes in the ampy system under different pH conditions, the crystal structure for the isolated m1-[Co(dien)(ampy)OP(OH)3]Cl3 · 2H2O species, and a rationale for its predominance at neutral pH based on internal H-bonding.
- Zhu, Tao,Jackson, W. Gregory,Hockless, David C.R.,Willis, Anthony C.
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p. 2210 - 2225
(2008/10/09)
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- Helicity interchange in the cadmium(II), mercury(II) and lead(II) complexes of 2 isomeric pendant arm tetraaza macrocyclic ligands
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In aqueous 0.10 mol*dm**-3 NEt4ClO4 at 298.2 K the complexes formed by Cd(2+), Hg(2+) and Pb(2+) with the isomeric ligands N,N',N'',N'''-tetrakis(2-methoxyethyl)-1,4,7,10-tetraazacyclododecane (TMEC-12) and N,N',N'',N'''-tetrakis((S)-2-hydroxypropyl)-1,4,
- Stephens, Ashley K. W.,Dhillon, Ramesh,Lincoln, Stephen F.,Wainwright, Kevin P.
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p. 185 - 188
(2008/10/08)
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- Equilibrium and Enthalpy Measurements on the Zinc(II) Chloride, Bromide and Iodide Systems in Acetonitrile and Pyridine, and on the Mercury(II) Chloride, Bromide and Iodide Systems in Acetonitrile
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The thermodynamics of the formation of chloride, bromide and iodide complexes of zinc (II) in acetonitrile and pyridine, and of mercury (II) in acetonitrile, have been determined at 25 deg C by means of potentiometric and calorimetric measurements.Pyridinium trifluoromethylsulfonate has been used as supporting electrolyte to an ionic strength of 0.1 M.The complex formation in the zinc(II) and mercury(II) halide systems is very strong in acetonitrile, and four complexes are formed for all halides of both metal ions.All zinc(II) halide complexes except the first bromide and iodide complexes are formed in exothermic reactions.All mercury (II) halide complexes are formed in strongly exothermic reactions.The stability constants observed in acetonitrile solution are large because acetonitrile solvates divalent ions poorly.The complex formation in the zinc(II) halides is considerably weaker in pyridine because of stronger solvation of the zinc(II) ion.Only two chloride and bromide and one iodide complex of zinc(II) are formed in pyridine.
- Persson, Ingmar,Dash, Kailash C.,Kinjo, Yoshiaki
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p. 433 - 442
(2007/10/02)
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- The solvolysis of metal fluorosulfates in trifluoromethyl sulfuric acid
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The quantitative conversion of fluorosulfates into trifluoromethyl sulfates is systematically investigated.The reaction proceeds initially according to the general equation where E is a coordinatively saturated metal or an organometallic moiety.However, the key to a quantitative substitution is the observed degradation of the SO3F group by excess HSO3CF3 and the noted observation of various volatile by-products that do not appear to interfere in the isolation of analytically pure trifluoromethyl sulfates.The fluorosulfates selected are representatives of the most common bond and coordination types - ionic or covalent with coordination through one, two, or three oxygens of the SO3F groups.The selected substrates display a fairly wide range of solubilities in HSO3F.All conversion attempts are successful except for one, that of polymeric Hg(SO3F)2, and a number of new SO3CF3 derivatives of tin, platinum, germanium, and palladium are described.The solvolysis of tin(IV) acetate in HSO3CF3 is reinvestigated and the synthesis of two other trifluoromethyl sulfuric acid derivatives, CsSO3CF3.HSO3CF3 and CH3CO2H.HSO3CF3, are described.
- Mallela, S. P.,Sams, J. R.,Aubke, F.
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p. 3305 - 3312
(2007/10/02)
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