The reaction of monohydride complexes the late transition metals with lanthanoid alkyl derivatives affords heterobimetallic compounds direct metal–metal bonds. These covalent bonds are strongly polar and can be considered as donor–acceptor

We report on the fabrication of a boron-based two-dimensional (2D) material via electron irradiation-induced cross-linking carborane self-assembled monolayers (SAMs) crystalline silver substrates. The SAMs 1,2-dicarba-closo-dodecarborane-9,12-dithiol (O9,12) were prepared flat substrates and irradiated with low-energy electrons, resulting in 2D nanomembrane. mechanical stability compact character nanomembrane improved by using...

Abstract The reaction of Grignard compounds 1‐bromo‐2,4,6‐diisopropylbenzene ( 1 ) or 1‐bromo‐2,6‐dimethylbenzene 2 ), formed in situ, with 2,6‐dibromopyridine the presence a catalytic amount [(dme)NiBr ] (dme = 1,2‐dimethoxyethane) and tricyclohexylphosphane (1:2 ratio) leads to corresponding monoarylated bromopyridines. These bromopyridines undergo Pd‐catalysed aryl amination (Buchwald−Hartwig amination) 2,6‐diisopropylaniline giving rise...

Activation of the Si−H bond is observed for 1, which obtained from reaction triallylborane with bis(dimethylsilyl)ethyne, as result neighboring three-coordinate boron atom [Eq. (1)]. Compound 1 undergoes facile intramolecular hydrosilylation without a catalyst (!) to give 2.

Cp glue: A chiral four-coordinate organolanthanoid complex, which has an unsupported metal–metal bond, reacts to give a lanthanoid–transition-metal cluster with two-electron multicenter bonds (see structure). The reaction proceeds through CH bond activation by the polar and affords 1,2-dimetallation of one ligand metallocene moiety.

Luminescence is observed in three novel macropolyhedral nineteen- and eighteen-vertex chalcogenaboranes: Se

Abstract The reaction of bis(silyl)ethynes 2 – 4 , bearing one, two and three hydrides at one the silicon atoms, with triallylborane 1 leads primarily to alkenes 5 8 11 respectively by 1,1‐allylboration. In these alkenes, diallylboryl silyl group or more SiH functions are in cis‐positions CC bond, giving rise formation an electron‐deficient SiHB bridge. This follows unambiguously from consistent set NMR data, particular observation isotope‐induced chemical shifts Δ 10/11 B( 29 Si)....

Die Umsetzung von Monohydridkomplexen später Übergangsmetalle mit Lanthanoidalkylen führt zu heterodimetallischen Verbindungen direkten Metall-Metall-Bindungen (siehe Schema). Diese kovalenten Bindungen sind stark polar und können als Donor-Akzeptor-Bindungen verstanden werden.

Abstract The reaction of various alkynyl(vinyl)silanes containing two alkynyl groups with 9‐borabicyclo[3.3.1]nonane (9‐BBN) proceeds by regioselective 1,2‐hydroboration the vinyl group in first step, followed intramolecular 1,1‐organoboration reactions to afford 1,6‐disilapentalene derivatives, fused silacarbacycles a silole unit. Similarly, analogous an alkynyl(allyl)silane gives 1,7‐disilaindene derivative. products were characterized multinuclear magnetic resonance ( 1 H, 11 B, 13 C and...

Abstract The origin of broadening 13 C(carborane) NMR signals 1,2‐, 1,7‐ and 1,12‐dicarba‐ closo ‐dodecaboranes(12) several diphenylsilyl derivatives has been examined in detail could be traced only partially to unresolved C– 11 B spin‐spin coupling. Other contributions the line widths arise from 1 H dipole‐dipole interactions and, particular, isotope‐induced chemical shifts Δ 10/11 B( C), observed here for carboranes first time. In case 1‐diphenylsilyl‐1,2‐dicarba‐ ‐dodecaborane(12),...

Opening up closo-cluster chemistry: The first representative of the seven-vertex closo monocarbaborane series, [closo-2-CB6H7]− ion (see structure), was isolated together with [closo-1-CB7H8]− from simple reactions between nido-1-CB8H12 and Et3N. Both ions exhibit high stability in air are potentially useful for weakly coordinating anion chemistry.

1-Boraadamantane 1 was treated with alkyn-1-ylsilanes 2 containing one or two Si[bond]H functions. Under mild conditions, the reaction gave 4-methylene-3-borahomoadamantane derivatives 4 quantitatively and selectively by 1,1-organoboration. An electron deficient Si-H-B bridge present in product. The analogous of an alkyn-1-yl-disilane 3 corresponding alkene derivative 5, however, without bridge. Evidence for given IR data, extensive set NMR spectroscopical data ((1)H, (11)B, (13)C, (29)Si...

Abstract The reactions of alkyn‐1‐yl(vinyl)silanes R 2 Si[CC‐Si(H)Me ]CHCH [R = Me (1a), Ph (1b)], Si[CC‐Si(Br)Me (2a), and alkyn‐1‐yl(allyl)silanes ]CH CHCH (R (3a), (3b)] with 9‐borabicyclo[3.3.1]nonane in a 1:1 ratio afford high yield the 1‐silacyclopent‐2‐ene derivatives 4a, b 5a, 1‐silacyclohex‐2‐ene 6a, b, respectively, all which bear functionally substituted silyl group 2‐position boryl 3‐position. This is result selective intermolecular 1,2‐hydroboration vinyl or allyl group,...

RuCl2(PPh3)3 (1), when heated with an equimolar amount of nido-5,6-C2B8H12 (2) in toluene for a few hours, effected rather unexpected polyhedral contraction 2 to give the new half-sandwich small ruthenacarborane closo-C2B4H6Ru(PPh3)2HCl (3) moderate yield along minor amounts two isomeric 11-vertex ruthenacarboranes [3-Cl-1-(η6-C6H5Me)-1,2,4-RuC2B8H9] (4) and [6-Cl-1-(η6-C6H5Me)-1,2,4-RuC2B8H9] (5) open MC2B8 cluster structure. These complexes were characterized by 1H, 13C, 11B NMR...

The use of the Diels–Alder reaction unsubstituted tetraazaporphine as dienophile with some dienes anthracene series for synthesis novel substituted tetraazachlorins, tetraazabacteriochlorins and tetraazaisobacteriochlorins is reported. condensation anthracene, 9,10-dimethyl- or 2,6-di(tert-butyl)anthracene in boiling chlorobenzene gives dibenzobarreleno-substituted tetraazachlorins 3–5 yields up to 71%. When AlCl3 was used catalyst 2,6-di(tert-butyl) corresponding cis-...

Compounds (E)- (1) and (Z)-1,6-bis(trimethylsilyl)-hexa-3-ene-1,5-diyne (2) react with triethylborane (3) by 1,1-ethylboration in a 1:1 or 1:2 molar ratio (in the case of 1), whereas 2 only product is formed. The analogous reactions 1 triallylborane (4) are more complex because competition between 1,1-allyl- 1,2-allylboration. Again, compound reacts one equivalent 4. In 1-boraadamantane (5), 1,1-organoboration takes place either at both C≡C bonds leading to compounds containing...

Trimethylborane (1), triethylborane (2), 1,3-dimethyl-1-boracyclopentane (3), 1-methyl-1- boracyclohexane (4), 9-methyl- and 9-ethyl-9-borabicyclo[3.1.1]nonane [5(Me) 5(Et)], 1- boraadamantane (6) were studied by 11 B 13 C NMR spectroscopy with respect to coupling constants 1 J( C, B) C). Results of DFT calculations at the B3LYP/6-311+g(d,p) level theory show satisfactory agreement experimental data. Hyperconjugation arising from C-C σ bonds adjacent tricoordinate boron atom is indicated, in...

Alkynylsilanes bearing one to four alkynyl groups at silicon, with organyl (Me, Ph, Vin), H, Cl and substituents n Bu, t C 6 H 4 -4-Me, 3-thienyl, CH 2 NMe the C≡C bond, were prepared, their 13 29 Si NMR data are reported. The results of X-ray structure analyses three representative derivatives [di(phenylethynyl)dimethylsilane, di(phenylethynyl) methyl(phenyl)silane, tri(phenylethynyl)methylsilane] presented. chemistry mono- dialkynylsilanes was further developed prepare compounds...

The reaction of the carborane nido-5,6-C2B8H12 (1) with PCl3 in dichloromethane presence a "proton sponge" [PS = 1,8-bis(dimethylamino)naphthalene], followed by hydrolysis mixture, resulted isolation eleven-vertex nido-phosphadicarbaboranes 7,8,9-PC2B8H11 (2) and 10-Cl-7,8,9-PC2B8H10 (10-Cl-2), depending on ratio reactants. Both these compounds can be deprotonated PS to give nido anions [7,8,9-PC2B8H10]− (2−) [10-Cl-7,8,9-PC2B8H9]− (10-Cl-2−). molecular geometries all were optimized ab...

Reactions of the [K]+ salts [nido-7,9-C2B9H12]- anion (2) and its C-phenylated derivative [7-Ph-nido-7,9-C2B9H11]- (4) with [OsCl2(PPh3)3] (3) proceed in benzene at ambient temperature formation 16-electron chlorohydrido-Os(IV) exo-nido complexes, [exo-nido-10,11-{(Ph3P)2OsHCl}-10,11-(mu-H)2-7-R-7,9-C2B9H8] (5: R = H; 6: Ph), along small amounts charge-compensated nido-carboranes [nido-7,9-C2B9H11PPh3] (7) [7-Ph-nido-7,9-C2B9H10PPh3] (8) as byproducts. However, when carried out under mild...

Abstract Deprotonation of Ap*pyH {Ap*pyH = (6‐methylpyridin‐2‐yl)‐[6‐(2,4,6‐triisopropylphenyl)‐pyridin‐2‐yl]‐amine} using KH leads to Ap*pyK which undergoes a clean salt metathesis reaction with [YbI 2 (thf) 4 ] and [EuI in THF forming[Yb (Ap*py) 3 I(thf)] [Eu I(thf)], respectively. The two Yb II centers [Yb are close proximity chemically different. Thus, an f‐block‐element–f‐block‐element coupling pattern was observed. low‐field 171 signal consists central singlet satellites integral...

The principles of a new α-shift correlation (ASC) NMR method are demonstrated on model series substituted derivatives o-carborane for which reliable data available. This graphical revealed an acceptable linear between α(11B) or α(13C) shifts and those induced by substituents in unsubstituted (u) positions the carborane cluster. linearity holds all nuclei involved skeletal bonding: Δδ(N)u = g × α (where N 11B, 13C, 1H). factor (slope line 102) becomes important measure sensitivity given cage...