Chemoselective boron-carbon bond cleavage by hydroboration of borirenes.

We report on the hydroboration of 1-[bis(trimethylsilyl)amino]-2,3-diethylborirene (3) with 9-borabicyclo[3.3.1]nonane (9-BBN), which led through ring-opening to an amino(vinyl)borane.

Synthesis, structure and reactivity of disila- and distanna ansa half-sandwich complexes of molybdenum and tungsten.

We present the synthesis and characterization of disila- and distanna ansa half-sandwich complexes of Group 6 transition metals. These compounds exhibit high ring strain within the ansa bridge, which is the key factor for the insertion of elemental chalcogens.

Synthesis, structure, and bonding of novel homodinuclear cobalt and nickel borylene complexes.

Herein we report for the first time full details on the synthesis and structural characterization of novel homodinuclear bridging cobalt and nickel borylene complexes containing bridging carbonyl ligands, an unusual coordination motif rarely before observed for homodinuclear borylene complexes. Furthermore, the homodinuclear nickel complex represents the first instance of a nickel borylene complex. Quantum chemical analyses of charge-density topology, electron localization function (ELF) and natural charges indicate the absence of direct metal-metal bonds in both the cobalt and nickel systems, in contradiction with electron counting.

Borylene-based direct functionalization of organic substrates: synthesis, characterization, and photophysical properties of novel pi-conjugated borirenes.

Room temperature photolysis of aminoborylene complexes, [(CO)(5)M=B=N(SiMe(3))(2)] (1: M = Cr, 2: Mo) in the presence of a series of alkynes and diynes, 1,2-bis(4-methoxyphenyl)ethyne, 1,2-bis(4-(trifluoromethyl)phenyl)ethyne, 1,4-diphenylbuta-1,3-diyne, 1,4-bis(4-methoxyphenyl)buta-1,3-diyne, 1,4-bis(trimethylsilylethynyl)benzene and 2,5-bis(4-N,N-dimethylaminophenylethynyl)thiophene led to the isolation of novel mono and bis-bis-(trimethylsilyl)aminoborirenes in high yields, that is [(RC=CR)(mu-BN(SiMe(3))(2)], (3: R = C(6)H(4)-4-OMe and 4: R = C(6)H(4)-4-CF(3)); [{(mu-BN(SiMe(3))(2)(RC=C-)}(2)], (5: R = C(6)H(5) and 6: R = C(6)H(4)-4-OMe); [1,4-bis-{(mu-BN(SiMe(3))(2)(SiMe(3)C=C)}benzene], 7 and [2,5-bis-{(mu-BN(SiMe(3))(2) ((C(6)H(4)NMe(2))C=C)}-thiophene], 8. All borirenes were isolated as light yellow, air and moisture sensitive solids. The new borirenes have been characterized in solution by (1)H, (11)B, (13)C NMR spectroscopy and elemental analysis and the structural types were unequivocally established by crystallographic analysis of compounds 6 and 7.

Complexes with dative bonds between d- and s-block metals: synthesis and structure of [(Cy3P)2Pt-Be(Cl)X] (X = Cl, Me).

A platinum-beryllium adduct (see structure) was prepared by the reaction of [Pt(PCy(3))(2)] and BeCl(2). Treatment with methyllithium resulted in ligand substitution at the beryllium center. Both complexes were structurally characterized and display unprecedented two-center two-electron bonds between a transition metal and beryllium.

High-performance air-stable n-channel organic thin film transistors based on halogenated perylene bisimide semiconductors.

The syntheses and comprehensive characterization of 14 organic semiconductors based on perylene bisimide (PBI) dyes that are equipped with up to four halogen substituents in the bay area of the perylene core and five different highly fluorinated imide substituents are described. The influence of the substituents on the LUMO level and the solid state packing of PBIs was examined by cyclic voltammetry and single crystal structure analyses of seven PBI derivatives, respectively. Top-contact/bottom-gate organic thin film transistor (OTFT) devices were constructed by vacuum deposition of these PBIs on SiO(2) gate dielectrics that had been pretreated with n-octadecyl triethoxysilane in vapor phase (OTS-V) or solution phase (OTS-S).

Reversible sigma-borane-to-borylene transformation: a little something for everyone.

A reaction with many facets: The facile dehydrogenative synthesis of a borylene complex (left in scheme) from a dihydroborane (right), proceeds reversibly at room-temperature. The implications of this reaction for the fields of inorganic, main-group, and hydrogen-storage chemistry are covered in this Highlight.

Dicyclohexyl(2',4',6'-triisopropylbiphenyl-2-yl)phosphine-dichlorophenylborane.

In the crystal structure of the title compound, C(39)H(54)BCl(2)P, the phospho-rus atom is coordinated by a dichloro-phenyl-borane unit. The substituted biphenyl group and the two cyclo-hexyl groups at the phospho-rus atom are arranged in such a way to avoid steric crowding in the mol-ecule as far as possible.

Enantioselective synthesis of tricyclic amino acid derivatives based on a rigid 4-azatricyclo[5.2.1.0]decane skeleton.

An enantioselective route to four tricyclic amino acids and N-tosylamides, composed of a central norbornane framework with a 2-endo,3-endo-annelated pyrrolidine ring and a 5-endo-C₁ or -C₂ side chain, has been developed. A key intermediate was the chiral, N-Boc-protected ketone (1R,2S,6S,7R)-4-azatricyclo[5.2.

Axially chiral beta,beta'-bisporphyrins: synthesis and configurational stability tuned by the central metals.

In this paper, the synthesis of a new type of intrinsically chiral, directly beta,beta'-linked, octa-meso-aryl-substituted bisporphyrins is described, by using an optimized Suzuki-Miyaura coupling procedure. This strategy leads to a broad variety of such axially chiral 'superbiaryls', differing in their metalation states and substitution patterns. On the basis of an efficient route to as-yet-unknown beta-boronic acid esters of various meso-tetraarylporphyrins (TAPs) by a two-step bromination-borylation protocol, 18 axially chiral bisporphyrin derivatives were prepared in good to excellent yields.

Comparative analysis of electron-density and electron-localization function for dinuclear manganese complexes with bridging boron- and carbon-centered ligands.

Bonding in borylene-, carbene-, and vinylidene-bridged dinuclear manganese complexes [MnCp(CO)(2)](2)X (X = B-tBu, B = NMe(2), CH(2), C=CH(2)) has been compared by analyses based on quantum theory of atoms in molecules (QTAIM), on the electron-localization function (ELF), and by natural-population analyses. All of the density functional theory based analyses agree on the absence of a significant direct Mn-Mn bond in these complexes and confirm a dominance of delocalized bonding via the bridging ligand. Interestingly, however, the topology of both charge density and ELF related to the Mn-bridge-Mn bonding depend qualitatively on the chosen density functional (except for the methylene-bridged complex, which exhibits only one three-center-bonding attractor both in -nabla(2)rho and in ELF).

Synthesis and structure of heterodinuclear rhodium and iridium borylene complexes.

Herein we report on the synthesis and structural characterization of a representative range of novel heterodinuclear bridging rhodium and iridium borylene complexes. The iridium borylene complexes feature an unusual coordination mode of the borylene ligand. Furthermore, the first instance of a heterodinuclear-bridged borylene compound containing a chromium atom in the three-membered ring is reported.

Direct functionalization at the boron center of antiaromatic chloroborole.

The presence of a reactive B-Cl bond allowed for the direct functionalization of the boron center in antiaromatic chloroborole ClBC4Ph4, thus allowing for a selective fine tuning of the optical properties of borole derivatives and facilitating a potential new approach toward the introduction of borole moieties into the backbone of organic pi-conjugated frameworks.

Reactivity of Pt0 complexes toward gallium(III) halides: synthesis of a platinum gallane complex and oxidative addition of gallium halides to Pt0.

The reaction of [Pt(PCy 3) 2] and GaCl 3 resulted in quantitative formation of the adduct [(Cy 3P) 2Pt-GaCl 3], the first known platinum gallane complex. Although similar reactivity with GaBr 3 and GaI 3 was expected, NMR spectroscopic data revealed a different reaction course. Crystal structure determination proved that, in the latter case, the product of the oxidative addition was formed.

[2]borametallocenophanes of group 4 metals: synthesis and structure.

We report a series of [2]borametallocenophanes of Ti, Zr, and Hf with various ligand systems. The ligands have been synthesized in high yields starting from 1,2-dibromo-1,2-bis(dimethylamino)diborane(4) upon reaction with Na[C5H5] and Li[C13H9], respectively. All compounds were fully characterized by multinuclear NMR spectroscopy and, for selected examples, by X-ray analysis.

Synthesis, reactivity, and electronic structure of [n]vanadoarenophanes: an experimental and theoretical study.

An optimized procedure for the selective dimetalation of [V(eta (6)-C 6H 6) 2] by BuLi/tmeda allowed for the isolation and characterization of [V(eta (6)-C 6H 5Li) 2].tmeda. X-ray diffraction of its thf solvate [V(eta (6)-C 6H 5Li) 2].

Synthesis and structure of a ferrocenylboron dication.

Treatment of the borane Br 2BFc (Fc = ferrocenyl) with the Lewis base 4-methylpyridine and Na[BAr (f) 4] [Ar (f) = 3,5-(CF 3) 2C 6H 3] afforded the boron dication [FcB(NC 5H 4-4-Me) 3][BAr (f) 4] 2. This compound is a rare example of a structurally characterized boron dication.

T-shaped platinum boryl complexes: synthesis and structure.

A series of cationic T-shaped 14-electron boryl complexes of the type trans-[(Cy3P)2Pt(B(X)X')]+ (X=Br; X'=ortho-tolyl, tBu, NMe2, piperidyl, Br; XX'=(NMe2)2, catecholato) were synthesized by halide abstraction from trans-[(Cy3P)2Pt(Br)(B(X)X')] (Cy=cyclohexyl) with Na[BArf 4] (Arf=3,5-(CF3)2C6H3), K[B(C6F5)4], or Na[BPh4]. X-ray diffraction studies were performed on all compounds, revealing a subtle correlation between the trans-influence of the boryl moiety and the Pt-H and Pt-C separations. However, no notable agostic C-H interaction with the platinum center was detected.

Synthesis of eta1-borazine complexes of palladium and platinum.

The eta(1)-borazine complexes trans-[(Cy(3)P)(2)M(Br)(Br(2)B(3)N(3)H(3))] (Cy = cyclohexyl) were prepared by oxidative addition of a B-Br bond of (BrBNH)(3) to [M(PCy(3))(2)] (M = Pd, Pt). Furthermore the platinum compound was converted into the T-shaped cationic complex trans-[(Cy(3)P)(2)Pt(Br(2)B(3)N(3)H(3))][BAr(f)(4)] [Ar(f) = 3,5-(CF(3))(2)C(6)H(3)] by addition of Na[BAr(f)(4)].

Synthesis and reactivity studies of iminoboryl complexes.

A range of new iminoborylcomplexes of the type [L(n)M-B[triple bond]N-R], which are isoelectronic with sigma-alkynyl complexes [L(n)M-C[triple bond]C-R], was obtained by systematically varying the metal M, the coligands L, and the nitrogen bound substituent R. Selected examples include, for example, trans-[(Cy3P)2(Br)Pt(B[triple bond]N iBu)], which is characterized by a sterically less demanding N-R group or the unprecedented rhodium species cis,mer-[(Br)2(Me3P)3Rh(B[triple bond]NSiMe3)]. All compounds were fully characterized in solution by multinuclear NMR spectroscopy and, where appropriate, in the solid state by X-ray crystallography.