The imido-hydrido complex (ArN)Mo(H)(Cl)(PMe(3))(3) catalyses a variety of hydroboration reactions, including the first example catalytic addition HBCat to nitriles form bis(borylated) amines RCH(2)N(BCat)(2). latter species easily undergoes chemoselective coupling with aldehydes R'C(O)H yield imines RCH(2)N=C(H)R'.

The nickel-catalyzed direct carboxylation of alkenes with the cheap and abundantly available C1 building block carbon dioxide (CO2 ) in presence a base has been achieved. one-pot reaction allows for selective synthesis wide range α,β-unsaturated carboxylates (TON>100, TOF up to 6 h(-1) , TON=turnover number, TOF=turnover frequency). Thus, it is possible, one step, synthesize sodium acrylate from ethylene, CO2 salt. Acrylates are industrially important products, which hitherto required multiple steps.

New Imido hydride complex 1 catalyzes a variety of silylation reactions that proceed via initial substrate activation but not silane addition.

Stoichiometric reaction of complexes (ArN)Mo(H)(Cl)(PMe₃)₃ (<bold>1</bold>) and (ArN)Mo(H)₂(PMe₃)₃ (<bold>3</bold>) with nitriles HBCat suggest that catalytic hydroboration reactions proceed <italic>via</italic> a series agostic borylamido borylamino complexes.

(POCN)Ni(<sc>ii</sc>) complexes were found to mediate a variety of carbonyl hydroboration reactions, including chemoselective benzaldehyde and hydroborative reduction amides.

The reaction of (ArN=)MoCl2(PMe3)3 (Ar = 2,6-diisopropylphenyl) with L-Selectride gives the hydrido-chloride complex (ArN=)Mo(H)(Cl)(PMe3)3 (2). Complex 2 was found to catalyze hydrosilylation carbonyls and nitriles as well dehydrogenative silylation alcohols water. Compound does not show any productive PhSiH3; however, a slow H/D exchange formation (ArN=)Mo(D)(Cl)(PMe3)3 (2D) observed upon addition PhSiD3. Reactivity toward organic substrates studied. Stoichiometric reactions benzaldehyde...

Abstract The readily synthesized and bench‐stable cobalt dichloride complex (dpephos)CoCl 2 is employed as a pre‐catalyst for diversity of silane additions to unsaturated organic molecules, including the normally challenging reduction amides amines. With regard hydrosilative even more effective activator free catalytic systems can be generated from bench‐stable, commercially available Co(acac) Co(OAc) with dpephos PPh 3 ligands. These operate under mild conditions (&lt;100 °C), many examples...

The development of efficient methodologies for production amines attracts significant attention from synthetic chemists, because serve as essential building blocks in the synthesis many pharmaceuticals, natural products, and agrochemicals. In this regard, deoxygenative reduction amides to by means transition-metal-catalyzed hydrogenation, hydrosilylation, hydroboration reactions represents an attractive alternative conventional wasteful techniques based on stoichiometric reductions...

The commercially available and bench-stable Co(acac)2 /dpephos system is employed as a precatalyst for selective efficient room temperature hydroboration of organic nitriles with HBPin to produce series N,N-diborylamines [RN(BPin)2 ], which react in situ aldehydes give aldimines. Formation aldimines from does not require dehydrating agent, applicable wide range N,N-diborylamine aldehyde substrates highly chemoselective, being unaffected by various common functional groups, such alkenes,...

Diagnostics for diagostics: The silylium ion 1 (see picture; C orange, Si red, H gray) is highly fluxional at room temperature but −80 °C exhibits a symmetric structure with three-center two-electron Si-H-Si bond supported by two additional Si←H-Si agostic interactions. In the related cation 2, SiH bonds coordinate equivalently to cationic silicon center afford symmetrical pentacoordinate ion. Supporting information this article available on WWW under...

An uncommon catalyst: The β-agostic NSiH⋅⋅⋅M complex 1 (Ar=2,6-diisopropylphenyl) catalyzes a variety of hydrosilylation reactions. Stoichiometric reactions with unsaturated compounds proceed via the silanimine intermediate A and, in case olefins or nitriles, give products SiC coupling, such as 2. Although agostic silylamido complexes have been known since 1992 (Scheme 1),1, 2 their reactivity has virtually unstudied, so they largely remain laboratory curiosity.3 We recently discovered...

The reaction of complex (ArN═)(2)Mo(PMe(3))(3) (Ar = 2,6-diisopropylphenyl) with PhSiH(3) gives the β-agostic NSi-H···M silyamido (ArN═)Mo(SiH(2)Ph)(PMe(3))(η(3)-ArN-SiHPh-H) (3) as first product. 3 decomposes in mother liquor to a mixture hydride compounds, including {η(3)-SiH(Ph)-N(Ar)-SiHPh-H···}MoH(3)(PMe(3))(3) characterized by NMR. Compound was obtained on preparative scale reacting 2 equiv under N(2) purging and multinuclear NMR, IR, X-ray diffraction. Analogous...

Carbonyl hydrosilylation catalyzed by (ArN)Mo(H)(SiH2Ph)(PMe3)3 (3) is unusual in that it does not involve the expected Si–O elimination from intermediate (ArN)Mo(SiH2Ph)(OiPr)(PMe3)2 (7). Instead, 7 reversibly transfers β-CH hydrogen alkoxide ligand to metal.

A molecule that releases the strong organometallic Lewis acid B(C(6)F(5))(3) upon irradiation with 254 nm light has been developed. This photo generator (PhLAG) now enables photocontrolled initiation of several reactions catalyzed by this important acid. Herein is described synthesis triphenylsulfonium salt a carbamato borate based on carbazole function, its establishment as PhLAG, and application photorelease to fabrication thin films polysiloxane material.

The increase in anthropogenic CO2 concentrations and associated environmental issues have demanded the development of technologies for utilization. Among various potential solutions to decrease emissions achieve carbon neutrality, recycling post-combustion into value-added chemicals fuels is considered one most economically attractive processes. In this regard, due its large global demand versatile applications chemical energy sectors, methanol serves as appealing target utilization CO2....

Reactions of bis(imido) compounds (RN)(2)Mo(PMe(3))(n) (n = 2, R (t)Bu; n 3, =2,6-dimethylphenyl (Ar') and 2,6-diisopropylphenyl (Ar)) (RN)(2)W(PMe(3))(3) (R 2,6-dimethylphenyl 2,6-diisopropylphenyl) with silanes afford four types products: the beta-agostic silylamido (RN)(eta(3)-RN-SiR'(2)-H...)MCl(PMe(3))(2) (M Mo W), mono(imides) (RN)MCl(2)(PMe(3))(3) silyl hydride derivative (ArN)(2)W(PMe(3))(H)(SiMeCl(2)), Si-Cl...W bridged product (ArN)(eta(2)-ArN-SiHMeCl-Cl...)WCl(PMe(3))(2)....

Treatment of ruthenium carbide (H2IMes)(Cl)2(PCy3)RuC (1) with the photoacid generator (PAG) [Ph3S][OTf] (3) under 254 nm light results in a highly efficient catalyst for ring-closing metathesis (RCM) and ring-opening polymerization (ROMP) reactions. The reactions proceed via formation phosphonium alkylidene complex [(H2IMes)(Cl)2Ru═C(H)PCy3][OTf] as active catalytic species. In case ROMP cycloalkenes, do not require addition PAG protonation 1 proceeds allylic C–H bond activation substrate UV light.

Selective hydroboration of isocyanates to formamides was demonstrated using a bench-stable and commercially available cobalt pre-catalyst. The deoxygenation N -methylamines performed under catalyst-free solvent-free conditions.

The reactions of bis(borohydride) complexes [(RN=)Mo(BH4)2(PMe3)2] (4: R = 2,6-Me2C6H3; 5: 2,6-iPr2C6H3) with hydrosilanes afford new silyl hydride derivatives [(RN=)Mo(H)(SiR'3)(PMe3)3] (3: Ar, R'3 H2Ph; 8: Ar', 9: (OEt)3; 10: HMePh). These compounds can also be conveniently prepared by reacting [(RN=)Mo(H)(Cl)(PMe3)3] one equivalent LiBH4 in the presence a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well exchange between ligand free Kinetic DFT...

Ein unüblicher Katalysator: Der β-agostische NSiH⋅⋅⋅M-Komplex 1 (Ar=2,6-Diisopropylphenyl) katalysiert eine Vielzahl an Hydrosilylierungen. Stöchiometrische Reaktionen von mit ungesättigten Verbindungen verlaufen über die Iminosilen-Zwischenstufe A und ergeben, im Fall Olefinen oder Nitrilen, Produkte einer Si-C-Kupplung wie 2.

A series of imino-POCNR, amino-POCNR2, and bis(phosphinite) POCOP pincer complexes Ni(II) were prepared tested in catalytic deoxygenative hydroboration amides with HBPin to the corresponding amines. In contrast hydrosilylation approach, primarily developed for tertiary amides, superior reactivity Ni-catalyzed was demonstrated secondary carboxamides. The hydride complex (POCOP)NiH proved most active these reactions, tolerating potentially reducible functionalities such as internal alkenes,...

Abstract Herein we describe an efficient methodology for metal‐free hydroborative cleavage of lactones and esters with HBPin (Pin=pinacol) to the corresponding alcohol derivatives using ammonia borane as a pre‐catalyst. The reactions proceed under mild conditions, can be performed in solvent‐free manner, do not require inert atmosphere. Combined experimental computational mechanistic studies suggest novel mechanism that involves μ‐aminodiboranes catalytically active species.

The European Union aims to be climate neutral by 2050. To achieve this ambitious goal, net greenhouse gas emissions must reduced at least 55% 2030. Post-combustion CO2 capture methods are essential reduce from the chemical industry, power generation, and cement plants. CO2, it captured then stored underground or converted into other valuable products. Apromising alternative for reduction is use of humic acid salts (HASs). This work describes a process preparation potassium (HmK) ammonium...