Abstract There have been a number of approaches developed for the catalyzed dehydrogenation amine–boranes as potential dihydrogen sources hydrogen storage applications in recent years. Key advances this area recently made thanks to catalytic and stoichiometric studies. In Minireview, fate upon coordination metal center is discussed with particular emphasis on BH activation pathways. We focus few cases which resulting dehydrogenated product could be achieved, includes aminoborane, simplest...

An efficient synthetic route to 2- and 2,7-substituted pyrenes is described. The regiospecific direct C-H borylation of pyrene with an iridium-based catalyst, prepared in situ by the reaction [{Ir(μ-OMe)cod}(2)] (cod = 1,5-cyclooctadiene) 4,4'-di-tert-butyl-2,2'-bipyridine, gives 2,7-bis(Bpin)pyrene (1) 2-(Bpin)pyrene (2, pin OCMe(2)CMe(2)O). From 1, simple derivatization strategies, we synthesized 2,7-bis(R)-pyrenes R BF(3)K (3), Br (4), OH (5), B(OH)(2) (6), OTf (7). Using these nominally...

Hydrogen, the simplest element in periodic table, plays a tremendous role organic and inorganic chemistry. For years, it was inconceivable that dihydrogen could be bound to metal center without breaking H−H bond. Thus, oxidative addition of H2 universally recognized as key elementary step hydrogenation processes. In 1984, Kubas co-workers reported first example complex which coordinated This opened new area coordination chemistry: σ-complexes were born, complementing well-known Werner-type...

One small step for ammonia–borane: The simplest elementary aminoborane compound H2BNH2, which results from dehydrogenation of ammonia–borane, has been trapped by a ruthenium complex fragment leading to the isolation bis(σ-BH) complex. analogous H2BNHMe and H2BNMe2 complexes were also prepared. (Picture: complex; Ru purple, P orange, N blue, B brown, H white.) Ammonia–borane attracted considerable interest recently as potential hydrogen source storage material owing its high capacity.1...

Abstract The Ir III fragment {Ir(PCy 3 ) 2 (H) } + has been used to probe the role of metal centre in catalytic dehydrocoupling H B⋅NMe ( A ultimately give dimeric aminoborane [H BNMe ] D ). Addition [Ir(PCy (H ][BAr F 4 1 ; Ar =(C 6 (CF ), gives amine‐borane complex H)][BAr a which slowly dehydrogenates afford BNMe )][BAr DFT calculations have mechanism dehydrogenation and show pathway featuring sequential BH activation/H loss/NH activation. results retrodimerisation . indicate that this...

A series of new dispiro[fluorene-9',6,9'',12-indeno[1,2b]fluorenes] (DSF-IFs) has been synthesised. These building blocks for blue-light-emitting devices and electroactive polymers combine indenofluorene (IF) spirobifluorene (SBF) properties. We report here our synthetic investigations towards these structures their thermal, structural, photophysical electrochemical properties have compared to those IF SBF. also the anodic oxidation DSF-IFs that leads formation non-soluble transparent...

Starting from RuHCl(H2)(PCy3)2, a terminal ruthenium mesitylborylene complex was obtained via double B−H bond activation of mesitylborane and concomitant release dihydrogen, such process being remarkably reversible.

The new borane complex RuH2(η2:η2-H2BMes)(PCy3)2 (2) can be isolated in good yield by reaction of H2BMes with RuH2(η2-H2)2(PCy3)2 (1) or alternatively, reacting the chloro dihydrogen RuHCl(η2-H2)(PCy3)2 (3) lithium mesitylborohydride. 2 has been fully characterized NMR and X-ray diffraction crystallography. A DFT/B3PW91 analysis shows that 2, group is coordinated to {RuH2(PCy3)2} fragment through two geminal σ-B−H bonds. This coordination involves σ-donation ruthenium π back-bonding from...

Abstract Zahlreiche Untersuchungen haben sich in jüngster Zeit mit der katalytischen Dehydrierung von Amin‐Boran‐Addukten beschäftigt, die als eine potenzielle Diwasserstoff‐Speicherform angesehen werden. Dabei wurden und stöchiometrischen Umsetzungen beachtliche Fortschritte erzielt. In diesem Kurzaufsatz werden Koordination an Metallzentren mögliche Folgereaktionen diskutiert, wobei ein besonderes Augenmerk auf B‐H‐Aktivierung liegt. Wir stellen wenigen Beispiele vor, denen...

The coordination chemistry of diisopropylaminoborane H2B−NiPr2 with valence isoelectronic metal fragments to form, essentially isostructural, [MH2(η2:η2-H2B−NiPr2)(PCy3)2]n+ (M = Ru, n 0; Rh and Ir, 1) has been explored by a combination X-ray crystallography, NMR spectroscopy, computational techniques. In the solid state solution aminoborane interacts centers through one four-center four-electron interaction, forming bis(σ-B−H) complexes. structural data point tighter interactions between...

Thermal decomposition of hindered amine-borane adducts leads in high yields to monomeric (dialkylamino)boranes R1R2N-BH2 (R1 and R2 = alkyl) that are new efficient boron-sources the Pd0 catalyzed borylation reaction affording aryl(dialkylamino)boranes R1R2N-BHR3 (R3 aryl).

A question of coordination mode: Two new borane compounds are prepared. They act as bifunctional ligands illustrated by their reaction with ruthenium polyhydrides which leads to the formation two complexes (see scheme) displaying either a delta-agostic interaction eta(2)-B-H bond involving trivalent boron atom or dihydroborate ligation.

The reaction of cyclodiborazane [Me(2)N-BH(2)](2) with the chloro(dihydrogen) ruthenium complex RuHCl(η(2)-H(2))(P(i)Pr(3))(2) (1) led to formation unsymmetricaly coordinated dimethylaminoborane RuHCl(H(2)BNMe(2))(P(i)Pr(3))(2) (2). coordination (H(2)BNMe(2)) center in 2 was carefully studied by combining X-ray, multinuclear NMR, and density functional theory (DFT) techniques, compared recently reported osmium analogue which originally formulated as a σ-B-H borinium...

Abstract Tuning the nature of linker in a L∼BHR phosphinoborane compound led to isolation ruthenium complex stabilized by two adjacent, δ‐CH and ε‐B sp2 H, agostic interactions. Such unique coordination mode stabilizes 14‐electron “RuH 2 P ” fragment through connected σ‐bonds different polarity, affords selective BH, CH, BC bond activation as illustrated reactivity studies with H boranes.

The solventless reaction of diisopropylaminoborane with n-butylamine, at room temperature, leads to a mixture B(sp2) H-, B(sp3) H2 -, and H3 -containing species. At low the outcome is completely modified, thus leading selectively formation high-mass polybutylaminoborane. When extended variety primary amines, under conditions this provides new, efficient, direct metal-free access high-molecular-mass polyaminoboranes in good high yields mild conditions.

A series of octupolar molecules derived from the boroxine framework were designed and their optical nonlinearities investigated by performing harmonic light scattering experiments in solution; found to combine excellent transparency near UV-visible region (lambdamax < or = 280 nm) significant first-order hyperpolarisabilities (up beta(0) 56 x 10(-30) esu).

A new type of carbene reaction is observed with the stable phosphinocarbene 1. It reacts benzonitrile to give 2H-azirine 2, which in dichloromethane converted into 1,2λ5-azaphosphete 3 after addition a catalytic amount dichloro(p-cymene)ruthenium(II). R = (c-C6H11)2N.

A series of new dispiro[fluorene-9',6,9' ',12-indeno[1,2b]fluorenes] (DSFIFs) that combine indenofluorene (IF) and spirobifluorene (SBF) architectural specificities have been prepared. Their anodic oxidations lead to the formation nonsoluble transparent polymers. The photophysical electrochemical properties these molecules evaluated for further blue OLED applications.

The synthesis of a new family boryl-substituted methylenephosphonium derivatives, the phosphorus analogues iminium salts, has been developed. They were used in preparation first stable boryl(phosphino)carbene, which fully characterized by NMR spectroscopy and X-ray crystallography. Density functional theory calculations indicate that these carbenes can be classified as push-pull with relatively small singlet-triplet energy gap.

The reactivity of the (o-phosphinophenyl)(amino)borane compound HB(NiPr2)C6H4(o-PPh2) prepared from Li(C6H4)PPh2 and HBCl(NiPr2) toward bis(dihydrogen) complex RuH2(H2)2(PCy3)2 (1) was studied by a combination DFT, X-ray, multinuclear NMR techniques including solid-state NMR, technique rarely employed in organometallic chemistry. study showed that RuH2{HB(NiPr2)C6H4(o-PPh2)}(PCy3)2 (3), isolated excellent yield as yellow crystals characterized X-ray diffraction, led solution to PCy3...

Dismembering molecules: The stable boryl(phosphino)carbene 1 can cleave small organic dioxide molecules. With CO2 and SO2, gives, respectively, the phosphacumulene ylide [Mes(iPr2N)B-O-P(CCO)(NiPr2)Mes] (see scheme structure) boryl(phosphoryl)sulfine [Mes(iPr2N)B-C(SO)-P(O)(NiPr2)Mes] which have been structurally spectroscopically characterized. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

Remote control: The title reaction is the first example of a catalyzed dehydrogenative cyclization (CDC) diamine–monoboranes to give cyclic diaminoboranes. strongly dependent on nature substitution pattern at remote amino group. Detailed facts importance specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by authors. Please note: publisher responsible for content functionality any supporting...

A series of borane bis(σ-B–H) ruthenium complexes RuH2(η2:η2-H2BR)(PR′3)2 (R = alkyl, aryl; R′ Cy, Cyp, iPr) has been prepared by using two synthetic strategies. The first one is based on a simple substitution reaction adding the corresponding monosubstituted H2BR to bis(dihydrogen) complex RuH2(η2-H2)2(PCy3)2. second one, more general, results from chloro RuHCl(H2)(PR′3)2 (R′ with lithium borohydrides RBH3Li Mes, tBu, Me, C4H3S, Ph). All have characterized multinuclear NMR, IR, and X-ray...