Simple two-coordinate acyclic silylenes, SiR(2), have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading B(NDippCH)(2) substituent (Dipp = 2,6-(i)Pr(2)C(6)H(3)), an isolable monomeric species, Si{B(NDippCH)(2)}{N(SiMe(3))Dipp}, can be synthesized which is stable in solid state up to 130 °C. This silylene species undergoes facile oxidative addition reactions with dihydrogen (at...

In the ten years since first examples of terminal borylene complexes were reported, rapid advances in chemistry this ligand class have been made, and parallels emerged with classical organometallic systems (such as carbenes, vinylidenes even CO) well other subvalent main group systems. This article reviews key developments synthetic, structural reaction chemistry, particular attention focusing on recent discoveries field.

Abstract An isolable phenylborylene species supported by two oxazol‐2‐ylidene ligands was synthesized and structurally characterized. Computational studies revealed the presence of lone‐pair electrons on boron atom in this molecule; therefore, there are eight around three‐coordinate center. The nucleophilic property confirmed reactions with trifluoromethanesulfonic acid [(thf)Cr(CO) 5 ], which gave corresponding conjugate a chromium–borylene complex, respectively.

The first example of a stable oxoborane monomer (LB=O) stabilized by complexation to AlCl3 has been prepared the reaction LAlCl2 with BCl3 followed treatment H2O in CH2Cl2 (L = [HC(CMe)2(NC6F5)2]). DFT calculations reveal that considerable boron-oxygen double bond character is retained this complex.

Synthetic approaches based on the direct borylation of ferrocene by BBr(3), followed boryl substituent modification, or lithiation derivatives and subsequent quenching with electrophile FBMes(2), have given access to a range derivatized Lewis acids which conduct systematic study fluoride cyanide binding. In particular, effects borane electrophilicity, net charge, ancillary ligand electronics/cooperativity binding affinities for these anions been probed combination NMR, IR, mass...

No CO: Fluoroborylene (BF), isoelectronic with CO and N(2), can be trapped by a transition metal. The structurally characterized complex [{CpRu(CO)(2)}(2)(mu-BF)] contains an unsupported bridging BF ligand, which is unprecedented in the structural chemistry of CO. With AlCl(3) , metal-bound coordinates through O atom without bond rupture, while more polar less pi-bonded ligand heterolytically cleaved (see picture).

The reaction of [Ir(coe)2Cl]2 (coe = cyclooctene) with the N-heterocyclic carbene N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) in tetrahydrofuran under anaerobic conditions leads to formation two main products, planar four-coordinate Ir(I) complex Ir(IPr)(IPr′′)Cl (1) formed by dehydrogenation one IPr isopropyl substituents (to give mixed NHC/alkene donor IPr′′) and trigonal bipyramidal Ir(III) system Ir(IPr)(aIPr)(H)2Cl (6), which features both "normal" "abnormal" C-bound isomers...

Abstract An isolable phenylborylene species supported by two oxazol‐2‐ylidene ligands was synthesized and structurally characterized. Computational studies revealed the presence of lone‐pair electrons on boron atom in this molecule; therefore, there are eight around three‐coordinate center. The nucleophilic property confirmed reactions with trifluoromethanesulfonic acid [(thf)Cr(CO) 5 ], which gave corresponding conjugate a chromium–borylene complex, respectively.

Autoxidation of polyunsaturated fatty acids (PUFAs) damages lipid membranes and generates numerous toxic by‐products implicated in neurodegeneration, aging, other pathologies. Abstraction bis‐allylic hydrogen atoms is the rate‐limiting step PUFA autoxidation, which inhibited by replacing hydrogens with deuterium (D‐PUFAs). In cells, presence a relatively small fraction D‐PUFAs among natural PUFAs sufficient to effectively inhibit peroxidation (LPO). Here, we investigate effect various on...

Chemically reinforced essential fatty acids (FAs) promise to fight numerous age-related diseases including Alzheimer's, Friedreich's ataxia and other neurological conditions. The reinforcement is achieved by substituting the atoms of hydrogen at bis-allylic methylene these FAs with isotope deuterium. This substitution leads a significantly slower oxidation due kinetic effect, inhibiting membrane damage. approach has advantage preventing harmful accumulation reactive oxygen species (ROS)...

The first example of a mononuclear boron dication has been prepared and isolated as the bis(trifluoromethanesulfonate) salt its 2,2'-bipyridine complex. compound [(HC(CMe)2(NC6F5)2(bipy)B][OTf]2 (1) was by treatment β-diketiminate-supported bis(trifluoromethylsulfonate) [(HC(CMe)2(NC6F5)2B(OTf)2] (2) with 2,2'-bipyridine. X-ray crystal structures 1 2 were determined, DFT calculations performed on [(HC(CMe)2(NC6F5)2B]2+.

Salt metathesis has been exploited in the synthesis of M-Al bonds, stabilized by a variety chelating N-donor substituents at aluminium and including first examples such systems featuring ancillary guanidinato frameworks. Importantly, this synthetic approach can be extended to σ-alane complexes through use hydride-containing transition metal nucleophiles. Cp'Mn(CO)(2)-[H(Cl)Al{(N(i)Pr)(2)CPh}] synthesized via route features an alane ligand bound more 'side-on' fashion than other complexes,...

Aminoboranes, H(2)BNRR', represent the monomeric building blocks from which novel polymeric materials can be constructed via metal-mediated processes. The fundamental capabilities of these compounds to interact with metal centers have been probed through coordination H(2)BNCy(2) at 16-electron [CpRu(PR(3))(2)](+) fragments. In contrast side-on binding isoelectronic alkene donors, an alternative mono(σ-BH) mode aminoborane ligation is established for H(2)BNCy(2), energies only ~8 kcal mol(-1)...

A coordinatively unsaturated dicationic phosphorus compound has been synthesized and characterized (see structure; P pink, N blue, C gray). DFT calculations revealed that the polycation should show superior Lewis acid σ-donor properties to corresponding bis(dimethylamino)phosphenium cations. Preliminary investigations with PMe3 confirmed unusual reactivity patterns for dication.

The first example of 1,2,4,3-triazaborole-based oxoborane has been synthesized via hydrogen migration upon the coordination AlCl3 to corresponding borinic acid. X-ray diffraction analysis and computational study disclosed partial B[double bond, length as m-dash]O double-bond property.

Abstract Reduction of indium boryl precursors to give two‐ and three‐dimensional M−M bonded networks is influenced by the choice supporting ligand. While unprecedented nanoscale cluster [In 68 (boryl) 12 ] − (with an In @In 44 concentric structure), can be isolated from potassium reduction a bis(boryl)indium(III) chloride precursor, analogous corresponding (benzamidinate)In III Br(boryl) system gives near‐planar (and weakly aromatic) tetranuclear 4 2− system.

The reaction of 1,3-dimesitylimidazolium chloride with Ti(NMe(2))(4) results in the 1,3-dimesitylimadazol-2-ylidene complex Ti(NMe(2))(2)Cl(2)(3); X-ray crystal structure 3 evidences short intramolecular Cl...C(carbene) contacts.

Cationic terminal borylene complexes, synthesized by halide abstraction, offer a versatile platform on which to gauge the effects electronic structure of metal−ligand bond brought about variation in substituent and metal/ligand framework. While exerts strong influence boron-centered electrophilicity hence π character length (e.g., from 1.792(8) Å for [Cp*Fe(CO)2(BMes)]+ 2.049(4) [CpFe(CO)2{B(NCy2)(4-pic)}]+), much smaller changes are effected set. Introduction stronger donor ruthenium-...

While N(2) and CO have played central roles in developing models of electronic structure, their interactions with transition metals been widely investigated, the valence isoelectronic diatomic molecules EX (E = group 13 element, X 17 element) yet to be isolated under ambient conditions, either as "free" molecule or a ligand simple metal complex. As part program designed address this deficiency, together wider issues chemistry cationic systems [L(n)M(ER)](+) B, Al, Ga; R aryl, amido, halide),...

Simple source: An intramolecular iridium-mediated CH borylation proceeds through transfer of a BH3 fragment from borohydride to benzylic carbon center (see scheme; coe=cyclooctene). and inexpensive LiBH4 is thus utilized as the boron source in CB conversion. Detailed facts importance specialist readers are published "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by authors. Please note: The publisher responsible for...

The synthesis of a class electron-rich amino-functionalized β-diketiminato (N-nacnac) ligands is reported, with two synthetic methodologies having been developed for systems bearing backbone NMe2 or NEt2 groups and range N-bound aryl substituents. In contrast to their (Nacnac)H counterparts, the structures protio-ligands feature bis(imine) tautomer CH2 group. Direct metalation lithium, magnesium, aluminium alkyls allows access respective metal complexes through deprotonation methylene...

Abstract Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me 3 Si) 2 N}M{B(NDippCH) }(thf) n (M=Ca, =2; M=Sr, =3), through reactions corresponding bis(amides), M{N(SiMe ) } (thf) , with Li‐ {B(NDippCH) }. Most notably, this approach can also be applied analogous potassium amide K{N(SiMe }, leading formation solvent‐free borylpotassium dimer [K{B(NDippCH) }] which is stable in solid state at room temperature for...

The reactions of terminal borylene complexes the type [CpFe(CO)2(BNR2)]+ (R = iPr, Cy) with heteroallenes have been investigated by quantum-chemical methods, in an attempt to explain experimentally observed product distributions. Reaction dicyclohexylcarbodiimide (CyNCNCy) gives a bis-insertion product, which 1 equiv carbodiimide is assimilated into each Fe═B and B═N double bonds form spirocyclic boronium system. In contrast, isocyanates (R′NCO, R′ Ph, 2,6-Xyl, Cy; Xyl C6H3Me2) react give...

Lewis acidic boranes containing the –BMes2 unit (Mes = 2,4,6-Me3C6H2) have been widely exploited in molecular sensors for fluoride ion reflecting, at least part, stability to air and moisture of derivatives type ArBMes2. In current study, binding capabilities simplest such system, PhBMes2 (1), investigated by spectroscopic crystallographic methods, with a view experimentally determining fundamental thermodynamic structural parameters associated this host/guest interaction. A constant, KF,...