A vinyl-functionalized all-cis-tetrasiloxycyclotetrasiloxane [ViSi(OSiMe2H)O]4 (Vi = vinyl group) Janus precursor was prepared from potassium cyclotetrasiloxane silanolate. The Janus precursor was selectively modified at its... more
A vinyl-functionalized all-cis-tetrasiloxycyclotetrasiloxane [ViSi(OSiMe2H)O]4 (Vi = vinyl group) Janus precursor was prepared from potassium cyclotetrasiloxane silanolate. The Janus precursor was selectively modified at its dimethylhydrosilyl groups [–SiMe2H] via the Piers–Rubinsztajn reaction to obtain a family of new tetravinyl-substituted Janus rings [ViSi(OR’)O]4 containing various functional groups in moderate yields. Remarkably, the tetravinyl groups on the structure remained intact after modification by the Piers–Rubinsztajn reaction. Since these synthesized compounds possess multiple functional groups (up to eight per molecule), they are potential precursors for advanced hybrid organic-inorganic functional materials.
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Carboxylic acid chlorides are useful substrates in organic chemistry. Many germanium analogues of carboxylic acid chloride have been synthesized so far. Nevertheless, all of the reported germathioacid chlorides use bidentate nitrogen... more
Carboxylic acid chlorides are useful substrates in organic chemistry. Many germanium analogues of carboxylic acid chloride have been synthesized so far. Nevertheless, all of the reported germathioacid chlorides use bidentate nitrogen ligands and contain germanium-nitrogen bonds. Our group synthesized germathioacid chloride, Ge(S)Cl{C6H3-2,6-Tip2}(Im-i-Pr2Me2), using N-heterocyclic carbene (Im-i-Pr2Me2). As a result of density functional theory (DFT) calculation, it was found that electrons are localized on sulfur, and the germanium-sulfur bond is a single bond with a slight double bond property.
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A perfect "Janus-cube" octasilsesquioxane, a nanometer-scale Janus particle with two different types of substituents, was synthesized through the cross-coupling of a "half-cube" cyclic sodium siloxanolate with another... more
A perfect "Janus-cube" octasilsesquioxane, a nanometer-scale Janus particle with two different types of substituents, was synthesized through the cross-coupling of a "half-cube" cyclic sodium siloxanolate with another half-cube cyclic fluorosiloxane. The structure was confirmed by X-ray crystallography to be a Janus cube. The overall synthesis is simple and does not require drastic separation methods compared with previous methods. The synthesis of the Janus cube demonstrates a novel siloxane bond-forming reaction involving the coupling a silanol salt and fluorosilane. The reaction is mild, does not result in acid generation, and could be applied to the construction of other novel siloxane compounds.
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The complex cation of the title compound, [NiCl{P(C6H4-2-S-i-Pr)3}](CF3SO3), has a slightly distorted trigonal–bipyramidal coordination geometry in which three S atoms are located in the equatorial plane, and one P and one Cl atom in the... more
The complex cation of the title compound, [NiCl{P(C6H4-2-S-i-Pr)3}](CF3SO3), has a slightly distorted trigonal–bipyramidal coordination geometry in which three S atoms are located in the equatorial plane, and one P and one Cl atom in the apical positions. In the cation, there are two intramolecular C—H...S hydrogen bonds. In the crystal, there are some intermolecular C—H...O and C—H...F hydrogen bonds formed between the cation and the anion. The trifluoromethanesulfonate anion and one of the methyl groups are both disordered over two sets of sites with occupancies of 0.629 (17):0.371 (17) and 0.786 (14):0.214 (14), respectively.
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... We recently synthesized an extremely hindered disilene (1) bearing an efficient steric protection group, 2,4,6-tris[bis(trimethylsilyl ... c) Suzuki, H.; Tokitoh, N ... have been obtained via dehydrohalogenation of the corresponding... more
... We recently synthesized an extremely hindered disilene (1) bearing an efficient steric protection group, 2,4,6-tris[bis(trimethylsilyl ... c) Suzuki, H.; Tokitoh, N ... have been obtained via dehydrohalogenation of the corresponding hydrochlorosilole with N-heterocyclic carbenes in ...
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New types of o-phenylene-bridged polythioethers tethered with extremely bulky aryl groups at their terminal sulfur atoms, such as TbtS(o-Phen)S(o-Phen)S(o-Phen)STbt (1) and TbtS(o-Phen)S(o-Phen)SS(o-Phen)S(o-Phen)STbt (2) (Tbt =... more
New types of o-phenylene-bridged polythioethers tethered with extremely bulky aryl groups at their terminal sulfur atoms, such as TbtS(o-Phen)S(o-Phen)S(o-Phen)STbt (1) and TbtS(o-Phen)S(o-Phen)SS(o-Phen)S(o-Phen)STbt (2) (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, o-Phen = o-phenylene), were synthesized and subjected to the complexation with several kinds of late-transition metals. In the case of polythioether 1, the reaction with RhCl3·3H2O in benzene/EtOH resulted in the formation of a
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ABSTRACT Reduction of dichloroplatinum complex dl-1 bearing two bulky aromatic substituents, Bbt groups (2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(tri-methylsilyl)methyl]phenyl), by sodium metal gave a unique platinacycle 2, a... more
ABSTRACT Reduction of dichloroplatinum complex dl-1 bearing two bulky aromatic substituents, Bbt groups (2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(tri-methylsilyl)methyl]phenyl), by sodium metal gave a unique platinacycle 2, a hydridoplatinum complex of [PtH{CH(2)SiMe(2)CH(SiMe(3))C(6)H(2)-3-CH(SiMe(3))(2)-5-C(SiMe(3))(3)-2-P(Me)CH(2)CH(2) (Me)Bbt}], which seems to be most likely formed via the initial formation of the corresponding Pt(0) complex and the subsequent intramolecular insertion of the Pt(0) center to the H-CH(2) bond of the o-bis(trimethylsilyl)methyl group of the Bbt group. On heating, the hydridoplatinum complex 2 underwent further intramolecular Si-C activation giving another type of platinacycle, [PtMe{SiMe(2)CH(SiMe(3))C(6)H(2)-3CH(SiMe(3))(2)-5-C(SiMe(3))(3)-2-P(Me)CH(2)CH(2)(Me)PBbt}] (4), which has a (methyl)(silyl)platinum complex structure.
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