109629-92-7Relevant academic research and scientific papers
Synthesis and Reactivity of Thiolate-Bridged NiIIMI Heterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2 Metalloligand
Kure, Bunsho,Sano, Mikie,Watanabe, Natsuki,Nakajima, Takayuki,Tanase, Tomoaki
, p. 4097 - 4109 (2017)
The mononuclear complex [Ni(meppp)] {H2meppp = meso-1,3-bis[(2-mercaptoethyl)(phenyl)phosphino]propane} was used as an S-bidentate NiP2S2 metalloligand to prepare a series of NiIIMI complexes with various neutral ligands, namely, [Ni(μ-meppp)ML2]PF6 [M = Rh, L = 1/2cod (1a; cod = 1,5-cycloocatadiene), CO (1b), XylNC (1c; Xyl = 2,6-dimethylphenyl), P(OPh)3 (1d); M = Ir, L = 1/2cod (2a), CO (2b), XylNC (2c)]. The reactivities of 1 and 2 toward methyl iodide and tertiary hydrosilanes were examined. Complexes 1c, 2a, and 2b reacted with MeI to afford the oxidative addition products [Ni(μ-meppp)M(L)2(Me)(I)]PF6 [M = Rh, L = XylNC (3c); M = Ir, L = 1/2cod (4a)] and [Ni(μ-meppp)Ir(CO)(Me)(I)2] (5). In the reactions with hydrosilanes, only 2c exhibited an interesting reactivity to afford the NiII(μ-H)IrIII silyl complexes [Ni(μ-meppp)(μ-H)Ir(XylNC)2(Si)]PF6 [Si = SiEt3 (6a), SiMe2Ph (6b), SiMePh2 (6c), SiPh3 (6d)]. The reaction proceeded via the intermediate isomers [Ni(meppp)(μ-H)Ir(XylNC)2(Si)]PF6 (7); intermediate 7d (Si = SiPh3) was characterized and has an NiII(μ-H)IrIII silyl structure with the hydrido ligand nesting in the reverse side of the Ni(μ-S)2Ir pocket to that of 6d. These results demonstrated that the reactivities of the bis(thiolate)-bridged NiIIMI heterodinuclear complexes can be tuned by changing the metal ions and ancillary ligands. In addition, the S-bidentate NiP2S2 metalloligand [Ni(meppp)] plays an important role in the stabilization of the bridging hydrido ligand in both pockets of the NiII(μ-H)IrIII core owing to the flexibility of the hinged Ni(μ-SR)2Ir structure.
Cationic rhenium(iii) complexes: synthesis, characterization, and reactivity for hydrosilylation of aldehydes
Pérez, Damaris E.,Smeltz, Jessica L.,Sommer, Roger D.,Boyle, Paul D.,Ison, Elon A.
, p. 4609 - 4616 (2017)
A series of novel cationic Re(iii) complexes [(DAAm)Re(CO)(NCCH3)2][X] [DAAm = N,N-bis(2-arylaminoethyl)methylamine; aryl = C6F5 (a), Mes (b)] [X = OTf (2), BArF4 [BArF4 = tetrakis[3,5-(trifluoromethyl)phenyl]borate] (3), BF4 (4), PF6 (5)], and their analogue [(DAmA)Re(CO)(Cl)2] [DAmA = N,N-bis(2-arylamineethyl)methylamino; aryl = C6F5] (6) were synthesized. The catalytic efficiency for the hydrosilylation reaction of aldehydes using 4a (0.03 mol%) has been demonstrated to be significantly more active than rhenium catalysts previously reported in the literature. The data suggest that electron-withdrawing substituents at the diamido amine ligand increase the catalytic efficiency of the complexes. Excellent yields were achieved at ambient temperature under neat conditions using dimethylphenylsilane. The reaction affords TONs of up to 9200 and a TOF of up to 126 h-1. Kinetic and mechanistic studies were performed, and the data suggest that the reaction is via a non-hydride ionic hydrosilylation mechanism.
Use of Silylated Formiates as Hydrosilane Equivalents
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Paragraph 0514, (2021/09/26)
The present invention relates to a method for preparing organic compounds of formula (I) by reaction between a silylated formiate of formula (II) and an organic compound in the presence of a catalyst and optionally of an additive. The invention also relates to use of the method for preparing organic compounds of formula (I) for the preparation of reagents for fine chemistry and for heavy chemistry, as well as in the production of vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, and pesticides.
Iron-Catalyzed Silylation of Alcohols by Transfer Hydrosilylation with Silyl Formates
Godou, Timothé,Chauvier, Clément,Thuéry, Pierre,Cantat, Thibault
, p. 2473 - 2477 (2017/10/26)
An iron catalyst is shown for the first time to promote transfer hydrosilylation with silyl formates and is utilized for the silylation of alcohols. Attractive features of this protocol include the use of an earth-abundant transition-metal catalyst, mild reaction conditions, and the release of gases as the only byproducts (H 2 and CO 2).
HYDROXIDE-CATALYZED FORMATION OF SILICON-OXYGEN BONDS BY DEHYDROGENATIVE COUPLING OF HYDROSILANES AND ALCOHOLS
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Paragraph 0148; 0149; 0151, (2017/02/28)
The present disclosure is directed to methods for dehydrogenatively coupled hydrosilanes and alcohols, the methods comprising contacting an organic substrate having at least one organic alcohol moiety with a mixture of at least one hydrosilane and sodium and/or potassium hydroxide, the contacting resulting in the formation of a dehydrogenatively coupled silyl ether. The disclosure further described associated compositions and methods of using the formed products.
Sodium Hydroxide Catalyzed Dehydrocoupling of Alcohols with Hydrosilanes
Toutov, Anton A.,Betz, Kerry N.,Haibach, Michael C.,Romine, Andrew M.,Grubbs, Robert H.
supporting information, p. 5776 - 5779 (2016/11/29)
An O-Si bond construction protocol employing abundantly available and inexpensive NaOH as the catalyst is described. The method enables the cross-dehydrogenative coupling of an alcohol and hydrosilane to directly generate the corresponding silyl ether under mild conditions and without the production of stoichiometric salt byproducts. The scope of both coupling partners is excellent, positioning the method for use in complex molecule and materials science applications. A novel Si-based cross-coupling reagent is also reported.
Silica-supported ultra small gold nanoparticles as nanoreactors for the etherification of silanes
Wang, Cui,Lin, Xijie,Ge, Yuzhen,Shah, Zameer Hussain,Lu, Rongwen,Zhang, Shufen
, p. 102102 - 102108 (2016/11/09)
Ultra small gold nanoparticles supported by porous silica (Au-SiO2) were successfully synthesized. Due to enrichment of reactants by silica, the Au-SiO2 particles functioned as nanoreactors for catalytic etherification of silanes wit
An Aluminum Hydride That Functions like a Transition-Metal Catalyst
Yang, Zhi,Zhong, Mingdong,Ma, Xiaoli,De, Susmita,Anusha, Chakkittakandiyil,Parameswaran, Pattiyil,Roesky, Herbert W.
supporting information, p. 10225 - 10229 (2015/09/01)
The reaction of [LAlH2] (L=HC(CMeNAr)2, Ar=2,6-iPr2C6H3) with MeOTf (Tf=SO2CF3) resulted in the formation of [LAlH(OTf)] (1) in high yield. The triflate substituent in 1 increases the positive charge at the aluminum center, which implies that 1 has a strong Lewis acidic character. The excellent catalytic activity of 1 for the hydroboration of organic compounds with carbonyl groups was investigated. Furthermore, it was shown that 1 effectively initiates the addition reaction of trimethylsilyl cyanide (TMSCN) to both aldehydes and ketones. Quantum mechanical calculations were carried out to explore the reaction mechanism.
Nonhydrolytic synthesis of silanols by the hydrogenolysis of benzyloxysilanes
Igarashi, Masayasu,Matsumoto, Tomohiro,Sato, Kazuhiko,Ando, Wataru,Shimada, Shigeru
supporting information, p. 429 - 431 (2014/04/17)
The hydrogenolysis of benzyloxysilanes was smoothly catalyzed by Pd/C in THF to give corresponding silanols under nonhydrolytic conditions. The reaction proved to be applicable to various benzyloxysilanes giving silanemonools, diol, and triol.
Trioxorhena(VII)carborane anion and its methyl-substituted analogue: Synthesis, structure, DFT, and catalytic studies
Pichaandi, Kothanda Rama,Fanwick, Phillip E.,Abu-Omar, Mahdi M.
scheme or table, p. 1888 - 1896 (2012/04/23)
Synthesis and characterization of trioxorhena(VII)carborane [Bu 4N][(η1-C2B9H 11)ReO3] (1a) and its methyl-substituted analogue [Bu 4N][(7,8-Me2-η1-C2
