Two reliable and efficient routes to bis(pentafluorophenyl)borane, 1, are described. A three-step procedure uses the −C6F5 transfer agent Me2Sn(C6F5)2 produce chloroborane ClB(C6F5)2, which is subsequently converted 1 by treatment with a silane, proceeds an overall yield of 62%. Alternatively, can be made in 69% from B(C6F5)3 Et3SiH heating two reagents at 60 °C for 3 days benzene. Borane dimeric solid state, as determined X-ray crystallographic analysis. However, aromatic solvents,...

We have presented new amino-NHC Ni−Al complex mediated para C−H bond activation for pyridine and quinolin, isolated the first time intermediate structure of a bimetallic η2,η1-pyridine nickel aluminum prior to its activation, which serves as key evidence catalysis.

We have developed a nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids to afford diarylmethanes and diarylethanes. This reaction proceeds under mild conditions exceptional functional group tolerance. Further, it transforms branched salts diarylethanes excellent chirality transfer, offering new strategy for the synthesis highly enantioenriched from readily available chiral amines.

The perimidine skeleton provides a framework for the isolation of novel, stable carbene possessing unique molecular architecture and electronic structure. remarkable steric environment exceptional electron-donating ability carbene-carbon are revealed through structural spectroscopic characterization parent two sterically encumbered rhodium-carbene complexes, L2RhCl{C[NCH(CH3)2]2(C10H6)} (5 L2 = COD; 6 L CO).

Reaction of {2,6-bis[2,6-(i-Pr)2PhNC(Me)]2(C5H3N)}VCl3·1.3(CH2Cl2) (1) with stoichiometric amount methyl alumoxane (PMAO) in toluene resulted the methylation pyridine ring ortho position affording {2,6-bis[2,6-(i-Pr)2PhNC(Me)]2(2-MeC5H3N)}VCl2·0.5 (toluene) (2). In process ligand became an anionic amide, one chlorine atom was eliminated by metal center, and vanadium coordination number decreased unit. This new trivalent compound is a potent ethylene polymerization precatalyst, polymers...

Reduction of a diazadiene chromium halide complex, [(HLiPr)Cr(μ-Cl)]2 (1, HLiPr = bis(2,6-diisopropylphenyl)diazadiene), with KC8 gave diamagnetic, bimetallic (HLiPr)2Cr2 (2). Complex 2 has been structurally characterized by X-ray crystallography and consists Cr2 unit spanned two ligands. The very short Cr−Cr distance (1.8028(9) Å) low formal oxidation state the Cr atoms suggest that bond order may be greater than 4. Spin-restricted spin-unrestricted DFT calculations on model complex both...

A convenient method for the systematic introduction of a variety organoimido ligands at terminal oxo sites in hexamolybdate cluster [Bu4N]2[Mo6O19] is described, consisting reaction with appropriate organic isocyanate RNCO (R = n-butyl, cyclohexyl, 2,6-diisopropylphenyl) pyridine solution. Singly functionalized imido-hexamolybdates [Mo6O18(NR)]2- incorporating each above substituents are described. In case 2,6-(diisopropyl)phenylimido ligand (NAr), multiple functionalization has also been...

Three hydrogen atoms participate in the unusual bond complex 1, which is obtained when rhenium compound cocrystallized with indole from benzene. The structure of 1 was elucidated by means neutron diffraction (HN …︁ HM distances 1.75 and 2.25 Å). energy determined IR spectroscopy (ΔH° = 4.3 ± 0.5 kcal mol−1). All these values were also reproduced theoretical calculations. Indole may be a useful additive for crystal growing general.

Herein, we provide crystallographic and computational evidence that Hashimoto's Rh2(S-PTTL)4 catalyst adopts a "chiral crown" conformation with reactive chiral face an unreactive achiral face. In Rh2(S-PTTL)4, all four tert-butyl groups are aligned on the same of catalyst, each C−(t-Bu) bond is roughly parallel to central Rh−Rh bond. This orients phthalimido opposite catalyst. Also described enantioselective diastereoselective protocol for intermolecular Rh2(S-PTTL)4-catalyzed...

Described is a scalable procedure for driving photochemical sytheses of trans-cyclooctene derivatives through metal complexation. During photoirradiation, reaction mixtures are continuously pumped column AgNO3-impregnated silica gel. The derivative selectively retained by the silica, but cis-isomer elutes from back to flask, where it photoisomerized and recirculated column. method provides access range usefully functionalized trans-cyclooctene, including 5-aza-trans-cyclooctene that...

Abstract A simple and convergent synthetic strategy used to increase the diversity of carbodicarbene ligand framework through incorporation unsymmetrical pendant groups is reported. Structural analysis spectroscopic studies ligands their Rh complexes are Reactivity reveal carbodicarbenes as competent organocatalysts for amine methylation using CO 2 a synthon. unique BH‐activated boron–carbodicarbene complex was isolated reaction intermediate, providing mechanistic insight into...

Abstract The reaction of 2‐[bis(2‐methoxy‐phenyl)phosphanyl]‐4‐methyl‐benzenesulfonic acid (a) and 2‐[bis(2′,6′‐dimethoxybiphenyl‐2‐yl)phosphanyl]benzenesulfonic (b) with dimethyl( N,N,N ′ ,N ′‐tetramethylethylenediamine)‐palladium(II) (PdMe 2 (TMEDA)) leads to the formation TMEDA bridged palladium based polymerization catalysts ( 1a 1b ). Upon pyridine, two mononuclear are formed 2a 2b These able homopolymerize ethylene also copolymerize acrylates or norbornenes. With ligand b , high...

Abstract The diastereoselective asymmetric synthesis of vicinal all‐carbon‐atom quaternary stereocenters is a challenging problem in organic for which only few solutions have been described. A catalytic Nazarov cyclization fully substituted dienones that provides cyclopentenone derivatives with high optical purity and as single diastereoisomers now reported.

The simple synthetic development of acyclic pincer bis(pyridine)carbodicarbene is depicted herein. Presented the first isolated structural carbodicarbene with a C-C-C angle 143°, larger than monodentate framework. More importantly, theoretical analysis showed that this embodies more allene-like character. Palladium complexes supported by ligand are active catalysts for Heck-Mizoroki and Suzuki-Miyaura coupling reactions.

The formation of a hitherto unknown three-coordinate dicationic hydrido boron complex is described. Interestingly, supporting ligand carbodicarbene gave unprecedented reaction with BH3 without using more highly electrophilic Lewis acid precursors. Spectroscopic, crystallographic, and computational analysis was performed to understand the electronic features these species.

Although gas adsorption properties of extended three-dimensional metal-organic materials have been widely studied, they remain relatively unexplored in porous molecular systems. This is particularly the case for coordination cages which surface areas are typically not reported. Herein, we report synthesis, characterization, activation, and a family carbazole-based cages. The chromium analog displays cage record BET (Brunauer-Emmett-Teller) area 1235 m2/g. With precise synthesis activation...

Porous molecular solids are promising materials for gas storage and separation applications. However, given the relative dearth of structural information concerning these materials, additional studies vital further understanding their properties developing design parameters optimization. Here, we examine a series isostructural cuboctahedral, paddlewheel-based coordination cages, M24(tBu-bdc)24 (M = Cr, Mo, Ru; tBu-bdc2– 5-tert-butylisophthalate), high-pressure methane storage. As decrease in...

Thiols can engage favorably with aromatic rings in S-H/π interactions, within abiological systems and proteins. However, the underlying bases for interactions are not well understood. The crystal structure of Boc-l-4-thiolphenylalanine tert-butyl ester revealed organization centered on interaction thiol S-H ring an adjacent molecule, a through-space Hthiol···Caromatic distance 2.71 Å, below 2.90 Å sum van der Waals radii H C. nature this was further examined by DFT calculations, IR...

Metal–organic frameworks and porous coordination cages have shown incredible promise as a result of their high tunability. However, syntheses pursuing precisely targeted mixed functionalities, such multiple ligand types or mixed-metal compositions are often serendipitous, require postsynthetic modification strategies, based on complex design. Herein, we present new method for the controlled synthesis functionality metal–organic materials via preparation salts. More specifically, combination...

Abstract Recently, hydrogen‐bonded organic frameworks (HOFs) have emerged as a rapidly advancing class of porous materials with significant potential for applications in the absorption and detection various chemicals. Here, unique ability amide groups to form endless‐stacking H‐bonds is implemented design HOFs. Starting from benzene‐1,3,5‐tricarboxamide amide‐containing tribenzocyclynes foundational building blocks, diverse range HOFs featuring 1D, 2D, or 3D has been synthesized. Among...

The importance of atmosphere: reaction [(Et8-calix[4]tetrapyrrole)U(dme)][K(dme)] and [K(naphthalenide)] yields remarkable dimeric complexes, the structures which are dependent on atmospheric gases employed. Reaction under N2 leads to dinitrogen cleavage a μ-KN bridged dimer (see picture). In contrast, reactions performed in an Ar atmosphere promoted solvent deoxygenation, as well with silicon grease. dme=1,2-Dimethoxyethane.

Bis(guanidinate) titanium imido complexes [{(Me2N)C(NiPr)2}2TiNAr'] (Ar' = 2,6-Me2C6H3 (1a); C6F5 (1b)) are competent catalysts for the guanylation of a variety arylamines with carbodiimide. The reversible [2 + 2] addition iPrNCNiPr to 1b is demonstrated and proposed be part catalytic cycle. Compounds 1a also effective precatalysts transamination trialkylguanidines yield aryldialkylguanidines.

The paramagnetic CoIII imido complex 1 is stable enough to be structurally characterized by X-ray diffraction. However, in solution a primary CH bond of the ligand activated and gives 2, product formal insertion into methyl group (see scheme; Ad=adamantyl).

The synthesis and characterization of the C2v symmetric (dimethylsilanediylbis(9-fluorenyl))zirconium dichloride (I) dimethyl (II) are reported. crystal molecular structure II has been solved. catalyst system I/MAO II/MAO (MAO = methylalumoxane) produce high-molecular-weight atactic polypropylene at relatively high polymerization temperatures (M̄w (1−4) × 105 50 °C Al/Zr 1200) in good yields, providing a practical entry to this novel, elastomeric propylene homopolymer.

The complex [Ru2(μ-CO)(CO)4(μ-dppm)2] in acetone solution is an efficient catalyst for the reversible reaction between formic acid and hydrogen/carbon dioxide. Complexes identified during catalytic reactions include hydrido formato complexes [Ru2(μ-H)(μ-CO)(CO)4(μ-dppm)2]+, [Ru2(μ-HCO2)(CO)4(μ-dppm)2]+, [Ru2(μ-H)2(CO)4(μ-dppm)2], [Ru2H(HCO2)(CO)4(μ-dppm)2] coordinatively unsaturated [Ru2H(μ-H)(μ-CO)(CO)2(μ-dppm)2].