We report a trinuclear copper(II) complex, [(DAM)Cu3(μ3-O)][Cl]4 (1, DAM = dodecaaza macrotetracycle), as homogeneous electrocatalyst for water oxidation to dioxygen in phosphate-buffered solutions at pH 7.0, 8.1, and 11.5. Electrocatalytic 7 occurs an overpotential of 550 mV with turnover frequency ∼19 s–1 1.5 V vs NHE. Controlled potential electrolysis (CPE) experiments 11.5 over 3 h 1.2 8.1 40 min 1.37 NHE confirm the evolution Faradaic efficiencies 81% 45%, respectively. Rinse tests...

Carbon monoxide is a key C1 feedstock for the industrial production of hydrocarbons, where it used to make millions tonnes chemicals, fuels, and solvents per annum. Many transition metal complexes can coordinate CO, but formation new C-C bonds in well-defined compounds from scission subsequent coupling two or more CO moieties at centre remains challenge. Herein, we report use low-coordinate iron(II) selective homologation affording unusual squaraines iron carboxylates ambient temperature...

Abstract Complexes with terminal phosphanido (MPR 2 ) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of PP and PC bonds. We showcase here isolation characterization mononuclear phosphanide rhodium complexes ([RhTp(H)(PR )L]) that result from oxidative addition secondary phosphanes, a reaction was also explored computationally. These compounds active catalysts for dehydrocoupling PHPh Ph PPPh . The hydrophosphination dimethyl...

Abstract The first transition metal catalyzed hydrophosphination of isocyanates is presented. use low‐coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion into the P−H bond diphenylphosphine yield phosphinodicarboxamides [Ph 2 PC(=O)N(R)C(=O)N(H)R], a new family derivatized organophosphorus compounds. This remarkable result can be attributed nature centers whose inherent electron deficiency enables Lewis‐acid mechanism in which combination steric pocket...

Two- and three-coordinate m-terphenyl complexes of manganese iron are efficient catalysts for the selective cyclotrimerisation primary aliphatic isocyanates affording isocyanurates in short reaction times under mild conditions.

Abstract Compounds of the late transition metals with MX multiple bonds (X=CR 2 , NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but noticeable gaps in second‐ and third‐row elements. For example, there are no isolated examples terminal imido rhodium complexes known to date. Described herein is isolation, characterization, some preliminary reactivity studies first [Rh(PhBP 3 )(NR)] (PhBP =PhB{CH PPh } ) RhN bond. These compounds result from reactions...

Group 1 salts containing carbazolido NNN pincer ligands are precatalysts for the dehydrogenation of Me2NH·BH3. NMR monitoring and DOSY studies show a heavy dependence on metal solvent, allowing in some cases selective formation products consistent with hydrogen liberation.

Abstract Herein we report the synthesis of three heteroleptic first‐row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to corresponding metal(I)‐carbonyl via a reductive carbonylation route. These are precatalysts for hydrophosphination activated alkenes, affording cobalt‐catalysed process that solely selectively yields β addition (anti‐Markovnikov) product. The scope this transformation has been investigated using variety alkenes. Isolation...

We report the synthesis, characterization, and electrocatalytic water oxidation activity of two cobalt complexes, (6-FP)Co(NO3)2 (1) (6-FP = 8,8′-(1,2-phenylene)diquinoline) (5-FP)Co(NO3)2 (2) (5-FP 1,2-bis(N-7-azaindolyl)benzene), containing "capping arene" bidentate ligands with nitrogen atom donors. The complexes 1 2 were supported on ordered mesoporous carbon (OMC) by π–π stacking, resulting in heterogenized materials 6-FP-Co-OMC-1 5-FP-Co-OMC-2, respectively, studied for oxidation. find...

A magnesium complex (1) featuring a bidentate aminopyridinato ligand is remarkably selective catalyst for the dehydrocoupling of amine-boranes. This reaction proceeds to completion with low loadings (1 mol %) under mild conditions (60 °C), exceeding previously reported s-block systems in terms selectivity, rate, and turnover number (TON). Mechanistic studies by situ NMR analysis reveals be first order both substrate. mechanism proposed account these findings, high TON attributed nature...

Low-coordinate <italic>m</italic>-terphenyl complexes are precatalysts for dehydrocoupling of dimethylamine–borane, where small changes in coordination environment effect significant mechanistic differences.

Abstract The feasibility of oxidative addition the P−H bond PHPh 2 to a series rhodium complexes give mononuclear hydrido‐phosphanido has been analyzed. Three main scenarios have found depending on nature L ligand added [Rh(Tp)(C H 4 )(PHPh )] (Tp= hydridotris(pyrazolyl)borate): i) clean and quantitative reactions terminal [RhTp(H)(PPh )(L)] (L=PMe 3 , PMe Ph ), ii) equilibria between Rh I III species: )(L)]⇄[RhTp(PHPh (L=PMePh PPh ) iii) simple ethylene replacement rhodium(I) [Rh(κ...

Olefin hydrophosphanation is an attractive route for the atom-economical synthesis of functionalized phosphanes. This reaction involves formation P–C and H–C bonds. Thus, complexes that contain both hydrido phosphanido functionalities are great interest development effective fast catalysts. Herein, we showcase excellent activity one them, [Rh(Tp)H(PMe3)(PPh2)] (1), in a wide range olefins. In addition to required nucleophilicity moiety accomplish bond formation, key role hydride ligand 1 has...

Abstract Compounds of the late transition metals with MX multiple bonds (X=CR 2 , NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but noticeable gaps in second‐ and third‐row elements. For example, there are no isolated examples terminal imido rhodium complexes known to date. Described herein is isolation, characterization, some preliminary reactivity studies first [Rh(PhBP 3 )(NR)] (PhBP =PhB{CH PPh } ) RhN bond. These compounds result from reactions...

Abstract Complexes with terminal phosphanido (MPR 2 ) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of PP and PC bonds. We showcase here isolation characterization mononuclear phosphanide rhodium complexes ([RhTp(H)(PR )L]) that result from oxidative addition secondary phosphanes, a reaction was also explored computationally. These compounds active catalysts for dehydrocoupling PHPh Ph PPPh . The hydrophosphination dimethyl...

The TBPY-5 rhodium complex [(PhBP3)Rh(CH2═CH2)(NCMe)] (1; PhBP3 = PhB(CH2PPh2)3), which contains ethylene in the equatorial plane and a labile acetonitrile ligand at one of axial positions, provides simple entry into chemistry fac-[P3Rh] scaffold. DFT calculations using model compound [(MeB(CH2PMe2)3)Rh(CH2═CH2)(NCMe)] (1′) reproduce well crystallographic geometry 1 converge to isolated conformer, strong π back-donation from metal π* orbital fixes it coplanar with plane. Oxidation is...

Abstract The reactions of the rhodium(I) and iridium(I) complexes [M(PhBP 3 )(C 2 H 4 )(NCMe)] (PhBP =PhB(CH PPh ) − with alkynes have resulted in synthesis a new family pseudo‐tetrahedral complexes, )(RC≡CR′)] (M=Rh, Ir), which contain alkyne as four‐electron donor. these unusual compounds two‐electron donors (L=PMe , CN t Bu) produced change “donicity” from 4e to 2e donor give five‐coordinate complexes. These were final products iridium whereas further took place rhodium In particular,...

Abstract A combination of four‐electron donors, such as alkynes, with strongly donating and strong‐field scorpionate ligands is appropriate to create pseudotetrahedral rhodium(I) environments, found in [Rh(PhBP 3 )(HCCPh)], which promotes HC bond activation CC coupling reactions under very smooth conditions.

A two-coordinate Fe(II) m-terphenyl complex acts as a precatalyst for the hydroamination of isocyanates, affording urea and biuret derivatives, with product selectivity accomplished via modification reaction conditions. Using more nucleophilic amine facilitates insertion up to four isocyanates into N–H bond, triuret tetrauret derivatives.

Abstract The first transition metal catalyzed hydrophosphination of isocyanates is presented. use low‐coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion into the P−H bond diphenylphosphine yield phosphinodicarboxamides [Ph 2 PC(=O)N(R)C(=O)N(H)R], a new family derivatized organophosphorus compounds. This remarkable result can be attributed nature centers whose inherent electron deficiency enables Lewis‐acid mechanism in which combination steric pocket...

The attachment of molecular catalysts to conductive supports for the preparation solid‐state anodes is important development devices electrocatalytic water oxidation. and characterization three cyclopentadienyl iridium(III) complexes, Cp*Ir(1‐pyrenyl(2‐pyridyl)ethanolate‐κO,κN)Cl ( 1 ) (Cp* = pentamethylcyclopentadienyl), Cp*Ir(diphenyl(2‐pyridyl)methanolate‐κO,κN)Cl 2 ), [Cp*Ir(4‐(1‐pyrenyl)‐2,2′‐bipyridine)Cl]Cl 3 as precursors electrochemical oxidation catalysts, are reported. These...

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Two-coordinate transition metal complexes are exciting candidates for single-molecule magnets (SMMs) because their highly axial coordination environments lead to sizeable magnetic anisotropy. We report a series of five structurally related two-coordinate Fe(II) m-terphenyl (4-R-2,6-Xyl2C6H2)2Fe [R = tBu (1), SiMe3 (2), H (3), Cl (4), CF3 (5)] where, by changing the functionalisation para-substituent (R), we alter function. All field-induced magnets, with relaxation rates that well-described...

Piperazine rings are essential motifs frequently found in commercial drugs. However, synthetic methodologies mainly limited to N-substituted piperazines, preventing structural diversity. Disclosed herein is a straightforward catalytic method for the synthesis of complex C-substituted piperazines based on an uncommon head-to-head coupling easily prepared imines. This 100% atom-economic process allows selective formation sole diastereoisomer, broad substrate scope, and good functional group...