Facile metal-free splitting of molecular hydrogen (H2) is crucial for the utilization H2 without need toxic transition-metal-based catalysts. Frustrated Lewis pairs (FLPs) are a new class activators wherein interactions with both acid and base heterolytically disrupt hydrogen−hydrogen bond. Here we describe activation exclusively by boron-based acid, perfluoropentaphenylborole. This antiaromatic compound reacts extremely rapidly in solution solid state to yield boracyclopent-3-ene products...

The synthesis and characterization of a stable, acyclic two-coordinate silylene, Si(SArMe6)2 [ArMe6 = C6H3-2,6(C6H2-2,4,6-Me3)2], by reduction Br2Si(SArMe6)2 with magnesium(I) reductant is described. It features V-shaped silicon coordination S–Si–S angle 90.52(2)° an average Si–S distance 2.158(3) Å. Although it reacts readily alkyl halide, does not react hydrogen under ambient conditions, probably as result the ca. 4.3 eV energy difference between frontier lone pair 3p orbitals.

A wide range of structurally characterized adducts CO₂are discussed in this review, from the strongly bound, charge assisted carbamate complexes through weaker halide and pseudo-halide to weakest possible inclusion complexes.

The synthesis and spectroscopic structural characterization of an extensive series acyclic, monomeric tetrylene dichalcogenolates formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch O, S, or Se; Ar bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features-the most notable which is their strong tendency display acute interligand, Ch-M-Ch, bond angles that often well below 90°. Furthermore, contrary normal steric expectations, the...

The reaction of :AlAr

The electronic structures of 15 group 13−16 carbene analogues are analyzed using various quantum chemical methods and compared to the data obtained for parent N-heterocyclic (NHC), imidazol-2-ylidene. results this study present a uniform analysis similarities differences in p-block main-group analogues. Though all systems formally isovalent, theoretical analyses unambiguously indicate that their run gamut from CC localized (group 13) CN 16) via intermediate, more delocalized, systems. In...

The reaction of Cp(x)(2)ZrCl(2) (Cp(x) = Cp, Cp*) with ammonia borane in presence n-butyllithium yielded Cp(2)Zr(Cl)NH(2)BH(3) and Cp(x)(2)Zr(H)NH(2)BH(3). These derivatives are isoelectronic the ethyl zirconocene chloride hydride, respectively, feature a chelating amidoborane ligand coordinating through Zr-N bond Zr-H-B bridge. In solution, each complexes consists an equilibrium mixture two isomers differing orientation respect to Zr-X (X H, Cl), while solid state, only one isomer was...

Treatment of toluene solutions the silylenes Si(SAr(Me6))2 (Ar(Me6) = C6H3-2,6(C6H2-2,4,6-Me3)2, 1) or Si(SAr(Pr(i)4))2 (Ar(Pr(i)4) C6H3-2,6(C6H3-2,6-Pr(i)2)2, 2) with excess ethylene gas affords siliranes (Ar(Me6)S)2SiCH2CH2 (3) (Ar(Pr(i)4)S)2SiCH2CH2 (4). Silirane 4 evolves spontaneously at room temperature in solution. A Van't Hoff analysis by variable-temperature (1)H NMR spectroscopy showed that ΔG(assn) -24.9(2.5) kJ mol(-1) for 4. computational study reaction mechanism using a model...

The perfluoro- and perprotiopentaphenylboroles 1 2 react with dihydrogen to effect H-H bond cleavage formation of boracyclopentene products. mechanism this reaction has been studied experimentally through evaluation the kinetic properties slower between H(2). is first-order in both [borole] [H(2)] activation parameters ΔH(‡) = 34(8) kJ/mol ΔS(‡) -146(25) J mol(-1) K(-1). A minimal isotope 1.10(5) was observed, suggesting an asynchronous geometry for rate-limiting transition state. To explain...

Abstract A Ni 0 ‐NCN pincer complex featuring a six‐membered N‐heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its II precursor. It retained chloride in the square‐planar coordination sphere nickel expected to be highly susceptible oxidative addition reactions. The rapidly activated ammonia at room temperature, ligand‐assisted process where carbon atom played unprecedented role proton acceptor. For first time, coordinated (ammine)...

Reduction of the aluminum iodide AlI2AriPr8 (1; AriPr8 = C6H-2,6-(C6H2-2,4,6-Pri3)2-3,5-Pri2) with 5% w/w Na/NaCl in hexanes gave a dark red solution from which monomeric alanediyl :AlAriPr8 (2) was isolated ca. 28% yield as yellow-orange crystals. Compounds 1 and 2 were characterized by X-ray crystallography, electronic NMR spectroscopy, theoretical calculations. The Al atom is one-coordinate, compound displays two absorptions its spectrum at 354 455 nm. It reacts H2 under ambient...

The perfluorinated boraindene was synthesized and fully characterized. Both computational crystallographic data show that is antiaromatic. Compound shown to react reversibly with H2 catalyse the hydrogenation of cyclohexene. mechanism catalysis probed experimentally computationally.

A new fluorescent terpyridyl-diphenylacetylene hybrid fluorophore 4'-[4-{(4-methoxyphenyl)ethynyl}phenyl]-2,2':6',2''-terpyridine, L, was synthesized via Sonogashira cross-coupling of 4'-(4-bromophenyl)-2,2':6',2''-terpyridine and 4-ethynylanisole in the presence Pd(PPh3)4/CuI as a catalyst. The solid state structure L shows trans arrangement pyridine nitrogen atoms along interannular bond terpyridine domain. Five transition metal complexes {[FeL2](CF3SO3)2 (1), [ZnL2](ClO4)2 (2),...

Reaction of the diarylgermylene Ge(ArMe6)2 [ArMe6 = C6H3-2,6-(C6H2-2,4,6-(CH3)3)2] with tert-butyl isocyanide gave Lewis adduct species (ArMe6)2GeCNBut, in which ligand displays a decreased C–N stretching frequency consistent an n → π* back-bonding interaction. Density functional theory confirmed that HOMO is Ge–C bonding combination between lone pair electrons on germanium atom and orbital ligand. The complex undergoes facile C–H bond activation to produce new diarylgermanium...

Cyanide Hitches a Ride is by-product of the biosynthesis ethylene in plants and it has been somewhat puzzling how ion safely removed before can shut down enzymatic pathways by coordination to catalytic iron centers. A proposed mechanism implicated cyanoformate ion—essentially, weak adduct cyanide carbon dioxide—as initial product, although its lifetime was uncertain. Murphy et al. (p. 75 ; see Perspective Alabugin Mohamed ) crystallized this previously elusive found that solution-phase...

The reaction of the copper(I) β-diketiminate copper complex {(Cu(BDIMes))2(μ-C6H6)} (BDIMes = N,N′-bis(2,4,6-trimethylphenyl)pentane-2,4-diiminate) with low-valent group 13 metal β-diketiminates M(BDIDip) (M Al or Ga; BDIDip N,N′-bis(2,6-diisopropylphenyl)pentane-2,4-diiminate) in toluene afforded complexes {(BDIMes)CuAl(BDIDip)} and {(BDIMes)CuGa(BDIDip)}. These feature unsupported copper–aluminum copper–gallium bonds short metal–metal distances, Cu–Al 2.3010(6) Å Cu–Ga 2.2916(5) Å. Density...

The reaction of three equivalents LiCH(SiMe3)2 with TiCl3(NMe3)2 afforded the rare homoleptic Ti(III) alkyl Ti{CH(SiMe3)2}3 (1) which crystallized as blue needles in 32 % yield. Single crystal X‐Ray data for 1 showed a trigonal pyramidal coordination geometry around titanium, could be ascribed to weak interactions between C–H bonds and atom based on computational results. X‐band EPR spectroscopy give spectral parameters consistent proposed formulation. Solutions are unstable at room...

The synthesis of a transient cationic phosphaborene [(Mes*)P=B(CAAC)]+ (Mes* = 2,4,6,‐trit‐tert‐butylphenyl, CAAC cyclic alkylamino carbene) by halide abstraction from the B‐brominated analogue is reported. This species was found to undergo rapid and selective intramolecular aliphatic C–H bond activation yield phosphinoborenium cation, which undergoes facile deprotonation give base‐stabilized phosphaborene. Computational investigation mechanism indicates boron‐centred route with an...

The nature of weak interactions in dimers X(3)E...EX(3) (E = N-Bi, X F-I) was investigated by wave function and density functional theory (DFT)-based methods. Out the 20 systems studied, 10 are found to be bound at CP-MP2 LMP2 levels theory. Detailed partition interaction energy into different components revealed that dispersion is primary force holding together but there also exists an important ionic component whose contribution increases with increasing halogen size. As expected, standard...

Bent allenes: Theoretical calculations show that extremely bent allenes, cyclic or acyclic, adopt a ground state only bears formal relationship to classical allenes. Consequently, five-membered ring allenes favor carbene-like electronic structure and formally contain trivalent carbon(II) center (see figure). Detailed facts of importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited typeset. They made available submitted by the...

The electronic structures of known N-heterocyclic carbenes (NHCs) with boron, nitrogen, and phosphorus backbones are examined using quantum chemical methods compared to the experimental results computational data obtained for a classical carbon analogue, imidazol-2-ylidene. sigma-donor pi-acceptor abilities studied NHCs in selected transition-metal complexes evaluated variety approaches such as energy charge decomposition analysis, well calculated acidity constants carbonyl stretching...

The reaction of p-phenylenediamine with excess PCl3 in the presence pyridine affords p-C6H4[N(PCl2)2]2 (1) good yield. Fluorination 1 SbF3 produces p-C6H4[N(PF2)2]2 (2). aminotetra(phosphonites) p-C6H4[N{P(OC6H4OMe-o)2}2]2 (3) and p-C6H4[N{P(OMe)2}2]2 (4) have been prepared by reacting appropriate amount 2-(methoxy)phenol or methanol, respectively, triethylamine. reactions 3 4 H2O2, elemental sulfur, selenium afforded tetrachalcogenides, p-C6H4[N{P(O)(OC6H4OMe-o)2}2]2 (5),...

Dichalcogenido-imidodiphosphinates, [N(PR2E)2]− (R = alkyl, aryl), are chelating ligands that readily form cyclic complexes with main group metals, transition lanthanides, and actinides. Since their discovery in the early 1960s, researchers have studied structural chemistry of resulting metal (where E O, S, Se) extensively identified a variety potential applications, including as NMR shift reagents, luminescent photonic devices, or single-source precursors for sulfides selenides. In 2002,...