Zero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes.

The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance.

Dithiophosphonate-Protected Eight-Electron Superatomic Ag Nanocluster: Synthesis, Isomerism, Luminescence, and Catalytic Activity.

The structure-property relationship considering isomerism-tuned photoluminescence and efficient catalytic activity of silver nanoclusters (NCs) is exclusive. Asymmetrical dithiophosphonate NH[SP(OR)(-CHOCH)] ligated first atomically precise silver NCs [Ag{SP(OR)(-CHOCH)}]PF {where, R = Pr (), Et ()} were established by single-crystal X-ray diffraction and characterized by electrospray ionization mass spectrometry, NMR (P, H, H), X-ray photoelectron spectroscopy, UV-visible, energy-dispersive X-ray spectroscopy, Fourier transforms infrared, thermogravimetric analysis, etc. NCs and consist of eight silver atoms in a cubic framework and enclose an Ag@Ag-centered icosahedron to constitute an Ag core of symmetry, which is concentrically inscribed within the S snub-cube, P cuboctahedron, and the O truncated tetrahedron formed by 12 dithiophosphonate ligands.

A Simple Nickel Metal-Organic Framework-Catalyzed Borylation of Aryl Chlorides and Bromides.

We report a recyclable and efficient catalyst system based on a nickel-benzene tricarboxylic acid metal-organic framework (Ni-BTC MOF) for the borylation of aryl halides, including aryl chlorides, with (pinacolato)diboron, affording aryl boronate esters in high yields (up to >99% yield) with high selectivity. This protocol demonstrates broad functional group tolerance. Catalyst can be recyclable up to four times, and gram-scale reactions further highlights the usefulness of this method.

Synthesis of Alkyl and Aryl Boronate Esters via CeO-Catalyzed Borylation of Alkyl and Aryl Electrophiles Including Alkyl Chlorides.

A recyclable protocol using a CeO-nanorod catalyst for borylation of alkyl halides with Bpin (pin = OCMeCMeO) is reported. A wide range of synthetically useful alkyl boronate esters are readily obtained from primary and secondary alkyl electrophiles, including unactivated alkyl chlorides, demonstrating broad utility and functional group tolerance. Preliminary investigation revealed an involvement of in situ formed catalytically active boryl species.

Transition metal- and solvent-free -Markovnikov selective protoboration of alkenes with bis(pinacolato)diboron.

An efficient -Markovnikov selective transition metal- and solvent-free Lewis base-mediated protoboration of aromatic and aliphatic alkenes with bis(pinacolato)diboron (Bpin) as the boron reagent is reported. This protocol is practical and demonstrates broad substrate scope and good functional-group tolerance on alkenes to give synthetically useful alkyl boronate esters in excellent yields under mild reaction conditions. The gram-scale reaction further highlighted the usefulness of this method.

Tuning the Surface Functionality of FeO for Sensitive and Selective Detection of Heavy Metal Ions.

The functionalization of materials for ultrasensitive detection of heavy metal ions (HMIs) in the environment is crucial. Herewith, we have functionalized inexpensive and environmentally friendly FeO nanoparticles with D-valine (FeO-D-Val) by a simple co-precipitation synthetic approach characterized by XRD, FE-SEM, and FTIR spectroscopy. The FeO-D-Val sensor was used for the ultrasensitive detection of Cd, Pb, and Cu in water samples.

Recent advances in the chemistry of the phosphaethynolate and arsaethynolate anions.

Over the past decade, the reactivity of 2-phosphaethynolate (OCP), a heavier analogue of the cyanate anion, has been the subject of momentous interest in the field of modern organometallic chemistry. It is used as a precursor to novel phosphorus-containing heterocycles and as a ligand in decarbonylative processes, serving as a synthetic equivalent of a phosphinidene derivative. This perspective aims to describe advances in the reactivities of phosphaethynolate and arsaethynolate anions (OCE; E = P, As) with main-group element, transition metal, and f-block metal scaffolds.

First-Row d-Block Element-Catalyzed Carbon-Boron Bond Formation and Related Processes.

Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon-boron bond into a carbon-X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row d-block transition metals have become increasingly widely used as catalysts for the formation of a carbon-boron bond, a transformation traditionally catalyzed by expensive precious metals.

Transition metal chemistry of heavier group 14 congener triple-bonded complexes: syntheses and reactivity.

The diversification and synthetic utility of carbyne complexes in organometallic chemistry and catalysis are well recognized, but the syntheses of related heavier group 14 alkylidyne complexes are a recent advancement. A wide range of metal-ylidyne M[triple bond, length as m-dash]E (E = Si-Pb) complexes were synthesized and characterized spectroscopically. The synthetic methodology generally involves elimination or substitution chemistry between metallates and suitable group 14 precursors.

Bonding Relationship between Silicon and Germanium with Group 13 and Heavier Elements of Groups 14-16.

The topic of heavier main group compounds possessing multiple bonds is the subject of momentous interest in modern organometallic chemistry. Importantly, there is an excitement involving the discovery of unprecedented compounds with unique bonding modes. The research in this area is still expanding, particularly the reactivity aspects of these compounds.

A nano-catalytic approach for C-B bond formation reactions.

Herein, we present a chronological survey of the metal/metal oxide nanoparticle-catalysed borylation reactions. Transition metal-catalysed borylation is considered to be one of the most efficient methods for the synthesis of organoboron derivatives. Considering chemical and pharmaceutical processes, the major drawbacks of homogeneous catalysis are metal contamination in products and inability to recover catalysts for reuse, which limit its application industrially, in biomolecules, and materials science.

Acylboranes: synthetic strategies and applications.

An overview of the synthesis and chemistry of acylborane compounds is presented. Acylboranes are a rare class of boron compounds, previously proposed as intermediates in several transformations and considered to be difficult to prepare. Methodologies for the preparation of acylborane compounds are based on both electrophilic and nucleophilic sources of boron.

Zinc-Catalyzed Dual C-X and C-H Borylation of Aryl Halides.

A zinc-catalyzed combined C-X and C-H borylation of aryl halides using B2 pin2 (pin=OCMe2 CMe2 O) to produce the corresponding 1,2-diborylarenes under mild conditions was developed. Catalytic C-H bond activation occurs ortho to the halide groups if such a site is available or meta to the halide if the ortho position is already substituted. This method thus represents a novel use of a group XII catalyst for C-H borylation.

Iridium-catalyzed borylation of pyrene: irreversibility and the influence of ligand on selectivity.

The iridium-catalyzed borylation of pyrene, using 4,4'-dimethyl-2,2'-bipyridine as the ligand, in the presence of t-BuOK, gave a mixture of 2,4,7,9-tetrakis(Bpin)pyrene (c4) and its 2,4,7,10-isomer (m4) in a 2.2:1 ratio, and the selectivity of the Ir-catalyzed borylation of pyrene is kinetically determined and can be influenced to some extent by the nature of the ligand.

Efficient synthesis of aryl boronates via zinc-catalyzed cross-coupling of alkoxy diboron reagents with aryl halides at room temperature.

A zinc(II)/NHC system catalyzes the borylation of aryl halides with diboron (4) reagents in the presence of KOMe at rt. This transformation can be applied to a broad range of substrates with high functional group compatibility. Radical scavenger experiments do not support a radical-mediated process.

Zinc-catalyzed borylation of primary, secondary and tertiary alkyl halides with alkoxy diboron reagents at room temperature.

A new catalytic system based on a Zn(II) NHC precursor has been developed for the cross-coupling reaction of alkyl halides with diboron reagents, which represents a novel use of a Group XII catalyst for CX borylation. This approach gives borylations of unactivated primary, secondary, and tertiary alkyl halides at room temperature to furnish alkyl boronates, with good functional-group compatibility, under mild conditions. Preliminary mechanistic investigations demonstrated that this borylation reaction seems to involve one-electron processes.

Syntheses and characterization of new vinyl-borylene complexes by the hydroboration of alkynes with [(μ3-BH)(Cp*RuCO)2(μ-CO)Fe(CO)3].

Room temperature photolysis of a triply-bridged borylene complex, [(μ(3)-BH)(Cp*RuCO)(2)(μ-CO)Fe(CO)(3)] (1 a; Cp* = C(5)Me(5)), in the presence of a series of alkynes, 1,2-diphenylethyne, 1-phenyl-1-propyne, and 2-butyne led to the isolation of unprecedented vinyl-borylene complexes (Z)-[(Cp*RuCO)(2)(μ-CO)B(CR)(CHR')] (2: R, R' = Ph; 3: R = Me, R' = Ph; 4: R, R' = Me). This reaction permits a hydroboration of alkyne through an anti-Markovnikov addition. In stark contrast, in the presence of phenylacetylene, a metallacarborane, closo-[1,2-(Cp*Ru)(2)(μ-CO)(2){Fe(2)(CO)(5)}-4-Ph-4,5-C(2)BH(2)] (5 a), is formed.

Synthesis and structure of dirhodium analogue of octaborane-12 and decaborane-14.

We present the results of our investigation of a thermally driven cluster expansion of rhodaborane systems with BH(3)·THF. Four novel rhodaborane clusters, for example, nido-[(Cp*Rh)(2)B(6)H(10)], 1; nido-[(Cp*Rh)B(9)H(13)], 2; nido-[(Cp*Rh)(2)B(8)H(12)], 3; and nido-[(Cp*Rh)(3)B(8)H(9)(OH)(3)], 4 (Cp* = η(5)-C(5)Me(5)), have been isolated from the thermolysis of [Cp*RhCl(2)](2) and borane reagents in modest yields. Rhodaborane 1 has a nido geometry and is isostructural with [B(8)H(12)].

Theoretical and experimental investigations on hypoelectronic heterodimetallaboranes of group 6 transition metals.

Density functional theory (DFT) has been used to probe the bonding and electronic properties of dimolybdaborane [(Cp*Mo)(2)B(5)H(9)], 1 (Cp* = η(5)-C(5)Me(5)), and several other heterodimolybdaborane clusters, such as [(Cp*Mo)(2)B(5)(μ(3)-OEt)H(7)] (2), [(Cp*Mo)(2)B(5)(μ(3)-OEt)(n-BuO)H(6)] (3), [(η(5)-C(5)H(5)W)(2)B(4)H(4)S(2)] (4), and [(Cp*Mo)(2)B(4)H(4)E(2)] (5-7, where, for 5, E = S, for 6, E = Se, and for 7, E = Te). The DFT results were also used to address some key points such as (i) the metal-metal bond length, (ii) the location and number of bridging and terminal hydrogen atoms, (iii) the molecular orbital analysis, and (iv) the assignment of (11)B and (1)H NMR chemical shifts. These studies further provide meticulous insight into similarities and differences between various dimetallaborane clusters 1-7.

Synthesis and structural characterization of new divanada- and diniobaboranes containing chalcogen atoms.

The reaction of [Cp(n)MCl(4-x)] (M=V: n=2, x=2; M=Nb: n=1, x=0; Cp=η(5)-C(5) H(5)) with LiBH(4)⋅THF followed by thermolysis in the presence of dichalcogenide ligands E(2)R(2) (E=S, Te; R=2,6-(tBu)(2)-C(6)H(2)OH, Ph) and 2-mercaptobenzothiazole (C(7)H(5)NS(2)) yielded dimetallaheteroboranes [{CpV(μ-TePh)}(2)(μ(3) -Te)BH⋅thf] (1), [(CpV)(2)(BH(3)S)(2)] (2), [(CpNb)(2)B(4)H(10)S] (3), [(CpNb)(2)B(4)H(11)S(tBu)(2)C(6)H(2)OH] (4), and [(CpNb)(2)B(4)H(11)TePh] (5). In cluster 1, the V(2)BTe atoms define a tetrahedral framework in which the boron atom is linked to a THF molecule. Compound 2 can be described as a dimetallathiaborane that is built from two edge-fused V(2)BS tetrahedron clusters.

An eleven-vertex metallaborane with tetracapped pentagonal bipyramidal geometry.

A metallaborane of novel structure, [(Cp*Mo)(2)B(3)H(3)Se(2){Fe(CO)(2)}(2){Fe(CO)(3)}(2)] (2; Cp* = η(5)-C(5)Me(5)), with tetracapped pentagonal bipyramidal geometry, isolated from the reaction of [(Cp*Mo)(2)B(4)H(4)Se(2)], 1 with [Fe(2)(CO)(9)]; the title compound exhibit an 11-vertex closo-cage geometry, having eight skeletal electron pairs (sep) and 98 valence electrons, appropriate for its geometric structure.

C-H activation of arenes and heteroarenes by early transition metallaborane, [(Cp*Ta)2B5H11] (Cp* = η5-C5Me5).

C-H activation of arenes and heteroarenes has been achieved by a hydrogen rich tantalaborane cluster [(Cp*Ta)(2)B(5)H(11)] that leads to the formation of C-H functionalized products. Furthermore, we examined the reaction of substituted thiophene and pyrrole derivatives with tantalaborane which provided a convenient and efficient route to regio-defined C-H functionalized heteroarenes.