Rong Shang

Hiroshima University | HU · Graduate School of Science, Department of Chemistry

Stabilization of low oxidation gold anions as aurate or auride by organic ligands has long been a synthetic challenge, owing to the proneness of low-valent gold centres to cluster. Despite being the most electronegative metal, isolable gold(I) aurate complexes have only been obtained from a few σ-withdrawing organo- and organo-main group ligands. S...

Generation of dihydrogen from water splitting, also known as water reduction, is a key process to access a sustainable hydrogen economy for energy production and usage. The key step is the selective reduction of a protic hydrogen to an accessible and reactive hydride, which has proven difficult at a p-block element. Although frustrated Lewis pair (...

The typical aza-BODIPYs in the dye family are known for bright fluorescence, excellent stability, and tunable absorption wavelengths. Hence, these dyes are attracting the increasing attention. Aza-BODIPYs having the maxima absorption in the near-infrared (NIR) region (650-900 nm) are very favorable for bioimaging in vivo due to the less photo-damag...

A new efficient metal‐based frustrated Lewis pair constructed by (P t Bu 3 ) 2 Pt and B(C 6 F 5 ) 3 was designed through density functional theory calculations for the catalytic dehydrogenation of ammonia borane (AB). The reaction was composed by the successive dehydrogenation of AB and H 2 liberation, which occurs through the cooperative functions...

The ‘CPNR’ ligand may be viewed as being isolobal with fulminate, CNO, however attempts to prepare a complex of such a ligand resulted instead in a range of novel imino and aminophosphinocarbyne complexes. Sequential treatment of [Mo(≡CBr)(CO) 2 (Tp*)] (Tp* = hydrotris(dimethylpyrazolyl)borate) with n BuLi and ClP=NMes* (Mes* = C 6 H 2 t Bu 3 ‐2,4,...

Isolation and structural characterization of hypervalent electron-rich pentacoordinate nitrogen species have not been achieved despite continuous attempts over a century. Herein we reported the first synthesis and isolation of air stable hypervalent electron-rich pentacoordinate nitrogen cationic radical (11-N-5) species from oxidation of their cor...

Dipyrrolyldiketone difluoroboron complexes (BONEPYs) were synthesized by condensation of the corresponding pyrroles and malonyl chloride followed by treatment with BF3·OEt2. The aryl-substituted pyrrole is introduced to form a cyclic system in order to investigate anion binding studies. In BONEPYs 1–3 the o-H of the aryl group forms hydrogen bondin...

The coordination chemistry of our recently isolated bis(diphenylphosphinyl)-functionalized dipyrido-annulated NHC (N-heterocyclic carbene), dpaP2-NHC, towards copper(I) and silver(I) has been studied. Based on dpaP2-NHC, two dinuclear silver and copper complexes [2, (Ag2L2) and 3, (Cu2L2)], two tetranuclear copper complexes {4, [Cu4L2(NCMe)2] and 6...

Phosphine-functionalized N-heterocyclic carbene (NHC) ligands are known to complex group 11 metal centers to form multinuclear complexes with photoluminescence properties. This study reports a structurally rigid ortho-substituted dipyrido-annulated NHC with T-shape coordination geometry and its di- and tetranuclear gold(I) complexes. The free ligan...

Structurally characterized hexacoordinate organophosphorus compounds remain rare due to their highly reactive nature and thermal instability. Herein we report the first synthesis of a pair of O-facial and O-meridional hexacoordinate oxaphosphates (5B and 5D) obtained from the O-apical and O-equatorial β-hydroxyalkylphosphoranes 3 and 4. This was ac...

Direct structural evidence for group 11 metal-mediated B-B bond activation was obtained from reactions of the tri(tert-butyl)azadiboriridine (1) with AuCl(L) complexes. The AuCl(SMe2) reaction afforded [η²-B,B-B(tBu)N(tBu)B(tBu)]AuCl (2) by ligand displacement. More donating phosphines as co-ligands led to B–B bond cleavage accompanied by either ha...

Borverbindungen In ihrer Zuschrift auf S. 15436 berichten Y. Yamamoto et al. über die Isolierung einer gebogenen Bor-Kette, in der drei Boratome über Mehrfachbindungen ohne zusätzliche Liganden verknüpft sind. Diese Spezies kann auch als ein Bis(borylen)-stabilisiertes Borylen aufgefasst werden.

Boron Compounds In their Communication on page 15234 ff., Y. Yamamoto et al. report the isolation of a bent boron chain, in which three boron atoms are connected via multiple bonds without additional ligands. This species can also be viewed as a bis(borylene)-stabilized borylene.

A triaminotriborane(3) was isolated as purple crystals through a reduction of (TMP)BCl2 (TMP = 2,2,6,6- tetramethylpiperidino) by sodium naphthalenide. Single-crystal X-ray diffraction and computational studies of the obtained triaminotriborane(3) revealed a bent structure of the [B(NR2)]3 chain. The bond lengths between the central and terminal bo...

A triaminotriborane(3) was isolated as purple crystals through a reduction of (TMP)BCl2 (TMP = 2,2,6,6- tetramethylpiperidino) by sodium naphthalenide. Single-crystal X-ray diffraction and computational studies of the obtained triaminotriborane(3) revealed a bent structure of the [B(NR2)]3 chain. The bond lengths between the central and terminal bo...

The new sterically hindered piperidine analog, dispiro[cyclohexane-2,2'-piperidine-6',2″-cyclohexane] (CPC(H), 2), and its N-methylated derivative CPC(Me) (3) were synthesized from commercially available starting materials in short steps. The N-lithiated amide LiCPC (4) was also isolated from 2 as a cyclictrimer in single crystals and showed slight...

The first terminal manganese phosphinidene complex was quantitatively synthesized from a terminal alkylborylene complex. Its structure and bonding, as well as the reaction mechanism, were investigated through a combination of experimental and computational studies.

Der erste Manganphosphinidenkomplex wurde quantitativ aus einem terminalen Alkylborylenkomplex erhalten. Dessen Struktur, Bindungssituation sowie der zugrundeliegende Reaktionsmechanismus wurden durch eine Kombination experimenteller und theoretischer Studien untersucht.

Boryl, borylene, and base-stabilized borylene complexes of manganese and iron undergo a range of different reactions when treated with isonitriles including single, double, and partial isonitrile insertions into metal-boron bonds, ring formation, isonitrile coupling, and the liberation of new monovalent boron species. Two of the resulting cyclic sp...

A range of bis(alkylidynyl)phosphines RP{C[triple bond, length as m-dash]M(CO)2(Tp*)}2 (M = Mo, W; R = Cl, Ph, Cy; Tp* = hydrotris(dimethylpyrazolyl)borate) are obtained from the reactions of [M([triple bond, length as m-dash]CLi)(CO)2(Tp*)] with Cl2PR or alternatively via the palladium(0)-mediated reactions of [W([triple bond, length as m-dash]CBr...

A heterocyclic manganese complex () derived from a carbonyl-borylene coupling reaction undergoes isomerisation, during which the former borylene moiety migrates to the cyclopentadienyl ligand and inserts into a C-H bond. This reaction and a computational study of its mechanism are discussed.

The reactions of isonitriles with a variety of metalloboryl and metalloborylene species are shown to yield a range of products, none of which display the typical Lewis acid-base reactivity previously observed between such metal complexes and other Lewis bases. Insertions of one, or several, isonitriles into the metal-boron bond give cyclic and spir...

Terminal borylene complexes of group 6-10 metals have been prepared through a number of synthetic strategies, displaying a wide structural diversity with numerous coordination modes of the borylene ligand [:BR]. Earlier, amino-substituted borylenes were found to serve as borylene ligand transfer reagents to a range of organic and organometallic sub...

The M-(?2-BMn) complexes [(?5-C5H5)(OC)2Mn{?-B(Cl)(tBu)Au(PPh3)}] (2) can be functionalized via halogen displacement reactions to afford isostructural complexes [(?5-C5H5)(OC)2Mn{?-B(R)(tBu)Au(PPh3)}] (R = Ph, CCPh, NCS). They also react with coinage metal complexes [MCl(PPh3)] (M = Au, Ag and Cu) in the presence of halide abstraction reagents to a...

The terminal alkylborylene complex [(η5-C5H5)(OC)2MnBtBu] (1) reacts with trimethylphosphine and CO to form a borylene-carbonyl coupling product [(η5-C5H5)(OC)Mn{κ2-C,C′-C(O)B(tBu)(PMe3)C(O)}] (3). This reactivity can be extended to nitrogen- and carbon-based ligands to form similar complexes [(η5-C5H5)(OC)Mn{κ2-C,C′-C(O)B(tBu)(L)C(O)}] (L = DMAP,...

The first examples of σ-coordinated metal-haloboryl complexes have been synthesised. The haloboryl moiety may be functionalized by nucleophilic substitution reactions, by which more electron-withdrawing substituents may be installed at the boron center.

A comprehensive study has been carried out to investigate the metathesis reactivity of the terminal alkylborylene complex [(h5-C5H5)(OC)2Mn B(t Bu)] (1). Its reactions with 3,3',5,5'-tetrakis(trifluoromethyl)benzophenone, 4,4'-dimethylbenzophenone, 2-adamantanone, 4,4'-bis(diethylamino)benzophenone and 1,2-diphenylcyclopropene-3-one af-forded the m...

Stannylcarbynes [M(equivalent to CSnMe3)(CO)(2)(Tp*)] [M = Mo, W; Tp* = hydrotris-(dimethylpyrazol-1-yl)borate], which are readily obtained via the successive treatment of [M(equivalent to CBr)(CO)(2)(Tp*)] with "BuLi and ClSnMe3, serve as effective carbyne transmetalation agents for the preparation of heteronuclear molecular gold carbido complexes...

Cyclic complex 2 with bridging carbonyl ligands was synthesized from a facile and reversible intermolecular carbonyl-borylene ligand coupling reaction at room temperature. Complex 2 exhibits an unprecedented coordination mode for boron-metal complexes, which is also reflected in its remarkable (11) B NMR chemical shift of -57.2 ppm. Findings from s...

Der cyclische Komplex 2 mit verbrückenden Carbonylliganden wurde über eine reversible intramolekulare Kupplung von Carbonyl- und Borylenligand bei Raumtemperatur erhalten. 2 weist einen bislang unbekannten Koordinationsmodus für Metall-Bor-Komplexe auf, der u. a. in einer bemerkenswerten chemischen Verschiebung im 11B-NMR-Spektrum zum Ausdruck komm...

The successive treatment of [Mo(≡CBr)(CO)2{HB(pzMe2)3}] (1; pz = pyrazol-1-yl) with BuLi and B(OR)3 (R = Me, iPr) affords, via the lithiocarbyne complex [Mo(≡CLi)(CO)2{HB(pzMe2)3}] (2), the boratocarbynes Li[Mo{≡CB(OMe)3}(CO)2{HB(pzMe2)3}] (R = Me, Li[3a]; R = iPr, Li[3b]). The salt Li[3b] readily eliminates LiOiPr to afford the neutral boryl...

The sequential treatment of [Mo(≡CBr)(CO)2{HB(pzMe2)3}] (pz = pyrazol-1-yl) with nBuLi and ClBR2 (BR2 = B(NMe2)2, O2C6H4) in tetrahydrofuran provides the borylcarbyne complexes [Mo(≡CBR2)(CO)2{HB(pzMe2)3}], in contrast to the reactions of many haloborane electrophiles, which result in the formation of the hydroxypentylidyne complex [Mo{≡C(CH2)4OH}(...

The successive reactions of [Mo(≡CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with nBuLi and ClAPh3 (A = Ge, Sn, Pb) afford the carbyne complexes [Mo(≡CAPh3)(CO)2(Tp*)] but fail in the case of ClCPh3 and ClSiPh3. The silicon analog [Mo(≡CSiPh3)(CO)2(Tp*)] may, however, be obtained via a multistep Fischer-Mayr synthesis. [...

The successive reactions of [Mo(≡CBr)(CO)2(Tp*)] (1; Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with BuLi and N,N'-dimethylthiocarbamoyl chloride provides as intended, via formation of [Mo(≡CLi)(CO)2(Tp*)] (2a), the thiocarbamoyl alkylidyne complex [Mo{≡CC(=S)NMe2}(CO)2(Tp*)] (3). Although the yields are poor, anal. of the side products obtai...

Anthony Hill joined Gordon Stone's research group as a post-doctoral research assistant from 1986-8 in the halcyon days of the "E317" lab at the University of Bristol. The supportive environment of creative and imaginative synthetic design that Gordon fostered in Bristol was unparalleled, quite without apol. for the pursuit of curiosity-driven scie...

The reaction of [RuRCl(CO)(PPh3)2] (R = C6H5, CH═CHPh) with the Yamashita−Nozaki ligand C6H4{N(CH2PPh2)}2BH (dppBH) results in facile elimination of benzene or styrene and formation of the ruthenium [PBP]− pincer complex [Ru{κ3B,P,P′-dppB)Cl(CO)(PPh3)] via a stepwise sequence that recalls the formation of the ruthenaboratrane [Ru(CO)(PPh3){B(mt)3}]...

3-(Thiobenzyl)indene (2) was prepd. from lithium indenide and dibenzyl disulfide. Deprotonation with BuLi/TMEDA in THF and the addn. of FeCl2 gave the expected 1:1 mixt. of rac- and meso-bis(1-thiobenzylindenyl)iron(II) (3). 13C-NMR studies in THF suggest that 3 undergoes a ring-flipping process to interconvert rac- and meso-3. Complex 3 exhibits a...

Successive treatment of [Mo(≡CBr)(CO)2{HB(pzMe2)3}] (pz = pyrazol-1-yl) with nBuLi and mercuric chloride provides the bis(carbido)mercurial complex Hg[C≡Mo(CO)2{HB(pzMe2)3}]2, which is catalytically demercurated by [RhCl(CO)(PPh3)2] to provide the bis-carbyne (ethanediylidyne) compound (μ-C2)[Mo(CO)2{HB(pzMe2)3}]2.

The mixed triaminocyclopropenium cation bis(diisopropylamino)dimethylaminocyclopropenium was prepared from bis(diisopropylamino)chlorocyclopropenium by reaction with dimethylamine. It was isolated as the perchlorate salt and found to have a distorted structure in the solid state. Tris(diisopropylamino)cyclopropenium was prepared by reaction of pent...

MePh3P+Br-.1/2CHCl3, C19H18P+·Br-.0.5CHCl3, was obtained by recrystn. from wet chloroform/Et2O and crystd. as the CHCl3 hemisolvate. There are 2 independent cations and anions in the asym. unit along with 1 CHCl3 solvent mol. The Ph rings adopt a propellor conformation in both independent cations, but with opposite directions of rotation. [on SciF...