Cubane-type sulfido clusters containing noble metals are newcomers compared with the corresponding of first transition series and molybdenum, which have been extensively studied in relation to metalloenzymes industrial hydrodesulfurization catalysts. This Account reviews recent progress studies on synthesis reactivities these metal cubane-type clusters. One goals this new area lies development unique catalysis embedded robust redox-active cores. Rational synthetic approaches indispensable...

The metal–ligand bifunctional cooperation of protic N-heterocyclic carbene and pyrazole complexes bearing an NH unit at the position β to metal is surveyed.

N–N bond cleavage of hydrazines on transition metals is considerable importance in understanding the mechanism biological nitrogen fixation under ambient conditions. We found that a metal–ligand-bifunctional complex iron with pincer-type ligand bearing two proton-responsive pyrazole arms catalyzes disproportionation hydrazine into ammonia and dinitrogen. The NH groups ligands are crucial for reaction, which most likely occurs through multiple bidirectional proton-coupled electron transfer...

Abstract This Minireview provides an overview of the chemistry pyrazole and N‐heterocyclic carbene (NHC) complexes bearing NH group at β‐position to metal. The synthesis structures as well Brønsted acidic nature β‐NH are described in detail. These attractive candidates for novel metal–ligand cooperative bifunctional catalysts, which would benefit highly effective molecular energy transformations.

Treatment of the protic N-heterocyclic carbene (NHC) complex [Cp*RuCl(LH)] (2; LH = N-(2-pyridyl)benzimidazolin-2-ylidene-κ2N,C) with AgNO2 gives nitrosyl–imidazolyl [Cp*Ru(NO)(L)][OTf] (OTf OSO2CF3), which undergoes reversible protonation to afford NHC [Cp*Ru(NO)(LH)][OTf]2. The bifunctional 2 also catalyzes dehydrative condensation N-(2-pyridyl)benzimidazole and allyl alcohol, leading formation trans- cis-2-(1-propenyl)-N-(2-pyridyl)benzimidazole.

Metal–pyrazole concerto: Protic pyrazole complex 1 underwent reversible dehydrochlorination to give pyrazolato complexes 2 and 3. Hydrido 4 was obtained by transfer hydrogenation of 2. The metal–ligand bifunction evidenced these transformations successfully applied catalytic intramolecular hydroamination unactivated, ω-alkenic primary secondary amines. Detailed facts importance specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or...

Hydrogenation and protonation of parent imido complexes have attracted much attention in relation to industrial biological nitrogen fixation. The present study reports the structure properties highly unsaturated diiridium complex [(Cp*Ir)2(μ2-H)(μ2-NH)]+ derived from deprotonation a amido complex. Because Lewis acid–Brønsted base bifunctional nature metal–NH bond, promotes heterolysis H2 deprotonative N–H cleavage ammonia afford corresponding under mild conditions.

Abstract A new metal–ligand bifunctional, pincer‐type ruthenium complex [RuCl( L1‐H2 )(PPh 3 ) 2 ]Cl ( 1 ; =2,6‐bis(5‐ tert ‐butyl‐1 H ‐pyrazol‐3‐yl)pyridine) featuring two proton‐delivering pyrazole arms has been synthesized. Complex , derived from [RuCl (PPh ] with underwent reversible deprotonation potassium carbonate to afford the pyrazolato–pyrazole [RuCl(L1‐H)(PPh ). Further of and hexamethyldisilazide in methanol resulted formation bis(pyrazolato) [Ru(L1)(MeOH)(PPh smoothly reacted...

Thermal degradation of a bifunctional Ir complex with 1,2-diphenylethylenediamine (DPEN) framework was investigated, which is relevant to catalyst deactivation in the acceptorless dehydrogenation formic acid. The well-defined hydridoiridium 1b, derived from N-triflyl-1,2-diphenylethylenediamine (TfDPEN), proved be solely transformed at reflux temperature 1,2-dimethoxyethane (DME) into two iridacycles (2 and 3) via C–H bond cleavage ortho carbon atoms phenyl substituents on diamine backbone....

Bifunctional catalysts, in which two functionalities cooperate substrate activation and transformation, promote a number of chemical biological reactions quite efficiently. This perspective mainly describes our efforts to extend the concept metal/NH bifunctional mononuclear catalysts dinuclear systems. The late transition metal complexes with bridging sulfonylated nitrogen donors parent amides (NH2) are focused on particularly, while chemistry related nitrogen-bridged polynuclear is also mentioned.

Catalytic intramolecular cyclization of nonactivated aminoalkene with functional group compatibility provides an atom-economical and concise route to valuable nitrogen-containing heterocycles yet remains a challenge. In this paper, we report the detailed substrate scope mechanism catalytic hydroamination half-sandwich-type iridium pyrazolato complex have recently developed. This metal–ligand bifunctional catalyst promoted various primary secondary aminoalkenes at mild temperatures (50–110...

Abstract A reaction of a 2‐(imidazol‐1‐yl)methyl‐6‐(pyrazol‐3‐yl)pyridine with [RuCl 2 (PPh 3 ) ] resulted in tautomerization the imidazole unit to afford unsymmetrical pincer‐type ruthenium complex containing protic pyrazole and N‐heterocyclic carbene (NHC) arms. Deprotonation one equivalent base led formation NHC–pyrazolato , indicating that NHC arm is less acidic. When was treated two equivalents under H or 2‐propanol, hydrido 4 pyrazolato groups obtained through metal–ligand cooperation.

Cp*Ir complexes bearing a 2-picolinamide moiety serve as effective catalysts for the direct reductive amination of ketonic compounds to give primary amines under transfer hydrogenation conditions using ammonium formate both nitrogen and hydrogen source. The clean operationally simple transformation proceeds with substrate catalyst molar ratio (S/C) up 20,000 at relatively low temperature exhibits excellent chemoselectivity toward amines.

The hydrodefluorination of fluoroarenes with transfer hydrogenation catalysts using 2-propanol or potassium formate is described. With the aid metal/NH cooperation, C–N chelating Ir complexes derived from benzylic amines can efficiently promote reduction involving C–F bond cleavage under ambient conditions even in absence hydrosilanes H2 gas, leading to partially fluorinated products good yields and high selectivity.

A simple and efficient method to generate macrocyclic structures has been developed based on the dynamic behavior of linker bis(2,2,6,6-tetramethylpiperidin-1-yl)disulfide (BiTEMPS). The prime linear structure was transformed into a (macro)cycle using following sequence: 1) thiol-ene reaction with BiTEMPS derivative afford precursor, then 2) an entropy-driven transformation induced by diluting heating. radicals generated from upon heating are highly tolerant toward variety chemical species,...

Due to the increase in amount of produced epoxy resin waste, it is desirable recycle this material reduce burden on environment. Despite many studies focusing recovering fibers from composites, few have focused recycling itself. In study, we developed a new approach for decomposed amine-cured as an amine curing agent. Following decomposition nitric acid, nitrated and product was extracted acid solution. The resulting extract then hydrogenated convert nitro group into amino group,...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCatalytic N-N Bond Cleavage of Hydrazines at the Coordinatively Unsaturated Diruthenium Center in [Cp*Ru(.mu.-SR)2RuCp*] (Cp* = .eta.5-C5Me5; R Pri, 2,6-Me2C6H3) and Isolation of.mu.-Phenyldiazene Complexes [Cp*Ru(.mu.-PhN:NH)(.mu.-SR)2RuCp*]Shigeki Kuwata, Yasushi Mizobe, Masanobu HidaiCite this: Inorg. Chem. 1994, 33, 17, 3619–3620Publication Date (Print):August 1, 1994Publication History Published online1 May 2002Published inissue 1 August...

The reaction of [Cp*RhCl(2)](2) (Cp* = eta(5)-C(5)(CH(3))(5)) with 2 equiv p-toluenesulfonamide in the presence KOH resulted formation sulfonylimido-bridged dirhodium(III) complex [(Cp*Rh)(2)(mu-NTs)(2)] (1a; Ts SO(2)C(6)H(4)CH(3)-p). imido 1a reacted hydrogen donors such as H(2) and 2-propanol to give sulfonylamido-bridged dirhodium(II) [(Cp*Rh)(2)(mu-NHTs)(2)] (2). Treatment (amido)rhodium(II) O(2) regenerated (imido)rhodium(III) 1a. Complex also underwent reversible protonation afford...