A single-component ambiphilic system capable of the cooperative activation protic, hydridic and apolar HX bonds across a Group 13 metal/activated β-diketiminato (Nacnac) ligand framework is reported. The hydride complex derived from H2 shown to be competent catalyst for highly selective reduction CO2 methanol derivative. To our knowledge, this process represents first example type catalyzed by molecular gallium complex.

Abstract An einen Übersichtsartikel aus dem Jahre 2004 anknüpfend, wird hier über den strukturellen Aufbau, die Stabilität und Anwendungen moderner schwach koordinierender Anionen (weakly coordinating anions, WCAs) berichtet, aber auch Fortschritte der “klassischen” WCAs. In tabellarischer Form werden sowohl Ausgangsverbindungen zur Einführung einer Vielzahl von WCAs als deren physikochemische Eigenschaften zusammengefasst. Damit lässt sich für mögliche gut beurteilen, wie am besten in...

The least-coordinating anion [(R^FO)₃Al–F–Al(OR^F)₃]⁻ and its more Lewis-basic brother [F–Al(OR^F)₃]⁻ (R^F = C(CF₃)₃).

Reaction of [Ru(IPr)2(CO)H]BAr(F)4 with ZnEt2 forms the heterobimetallic species [Ru(IPr)2(CO)ZnEt]BAr(F)4 (2), which features an unsupported Ru-Zn bond. 2 reacts H2 to give [Ru(IPr)2(CO)(η(2)-H2)(H)2ZnEt]BAr(F)4 (3) and [Ru(IPr)2(CO)(H)2ZnEt]BAr(F)4 (4). DFT calculations indicate that activation at proceeds via oxidative cleavage Ru concomitant hydride transfer Zn. can also activate hydridic E-H bonds (E = B, Si), computed mechanisms for facile H/H exchange processes observed in 3 4 are presented.

Polymers with tailored architectures and degradability were prepared through thiocarbonyl addition ring-opening (TARO) atom-transfer radical polymerization (ATRP) using dibenzo[c,e]oxepin-5(7H)-thione (DOT), Cu(I)Br, tris[2-(dimethylamino)ethyl]amine (Me6TREN) as the thionolactone, catalyst, ligand, respectively, in combination a selection of acrylic comonomers. Although copolymers selectively degradable backbone thioesters low dispersities (1.10 ≤ D̵ 1.26) achieved DMSO, acetonitrile, or...

Salt metathesis has been exploited in the synthesis of M-Al bonds, stabilized by a variety chelating N-donor substituents at aluminium and including first examples such systems featuring ancillary guanidinato frameworks. Importantly, this synthetic approach can be extended to σ-alane complexes through use hydride-containing transition metal nucleophiles. Cp'Mn(CO)(2)-[H(Cl)Al{(N(i)Pr)(2)CPh}] synthesized via route features an alane ligand bound more 'side-on' fashion than other complexes,...

Photolytic ligand displacement and salt metathesis routes have been exploited to give access κ(1) σ-alane complexes featuring Al-H bonds bound [W(CO)(5)] [Cp'Mn(CO)(2)] fragments, together with a related κ(2) complex of [Cr(CO)(4)]. Spectroscopic, crystallographic, quantum chemical studies are consistent the alane ligands acting predominantly as σ-donors, resulting binding energies calculated be marginally greater than those found for dihydrogen complexes.

Abstract The modes of interaction donor‐stabilized Group 13 hydrides (E=Al, Ga) were investigated towards 14‐ and 16‐electron transition‐metal fragments. More electron‐rich N‐heterocyclic carbene‐stabilized alanes/gallanes the type NHC⋅EH 3 (E=Al or exclusively generate κ 2 complexes [M(CO) 4 (κ ‐H E⋅NHC)] with (COD)] (M=Cr, Mo), including first σ‐gallane complexes. β‐Diketiminato (′nacnac′)‐stabilized systems, {HC(MeCNDipp) }EH , show more diverse reactivity 6 carbonyl reagents. For }AlH...

The mononuclear N-heterocyclic carbene (NHC) copper alkoxide complexes [(6-NHC)CuOtBu] (6-NHC = 6-MesDAC (1), 6-Mes (2)) have been prepared by addition of the free carbenes to tetrameric tert-butoxide precursor [Cu(OtBu)]4, or protonolysis [(6-NHC)CuMes] (3), (4)) with tBuOH. In contrast relatively stable diaminocarbene complex 2, diamidocarbene derivative 1 proved susceptible both thermal and hydrolytic ring-opening reactions, latter affording [(6-MesDAC)Cu(OC(O)CMe2C(O)N(H)Mes)(CNMes)]...

The sequence of fundamental steps implicit in the conversion a dihydroborane to metal borylene complex have been elucidated for an [Ir(PMe3)3] system. B–H oxidative addition has applied first time aminodihydroborane, H2BNR2, leading generation rare example primary boryl complex, Ln(H)M{B(H)NR2}; subsequent dihydride proceeds via novel B-to-M α-hydride migration. latter step is unprecedented group 13 ligand systems, and remarkable offering α- substituent migration from Lewis acidic center as...

Thermally robust expanded ring carbene adducts of AlH3 have been synthesized with a view to probing their ligating abilities via Al–H σ-bond coordination. While κ2 binding the 14-electron [Mo(CO)4] fragment is readily demonstrated, interaction [Mo(CO)3] results in μ:κ1,κ1 and μ:κ2,κ2 bridging linkages rather than terminal κ3 binding.

Abstract A single‐component ambiphilic system capable of the cooperative activation protic, hydridic and apolar HX bonds across a Group 13 metal/activated β‐diketiminato (Nacnac) ligand framework is reported. The hydride complex derived from H 2 shown to be competent catalyst for highly selective reduction CO methanol derivative. To our knowledge, this process represents first example type catalyzed by molecular gallium complex.

We describe a combined experimental and computational study into the scope, regioselectivity, mechanism of catalytic hydrodefluorination (HDF) fluoropyridines, C5F5–xHxN (x = 0–2), at two Ru(NHC)(PPh3)2(CO)H2 catalysts (NHC IPr, 1, IMes, 2). The regioselectivity extent HDF is significantly dependent on nature NHC: with 1 C5F5N favored ortho-position gives 2,3,4,5-C5F4HN as major product. This reacts to 3,4,5-C5F3H2N 2,3,5-C5F3H2N, latter can also undergo further 3,5-C5F2H3N 2,5-C5F2H3N....

Cationic Ir(III) systems supported by a bis(expanded NHC) framework and featuring both agostic C–H cis alkyl/hydride ligand sets have been targeted protonation of the corresponding bis(alkyl) hydride complexes. Remarkably, steric shielding afforded NHC substituents is such that these related putative 14-electron cations are air moisture stable. In solution, degenerate fluxional exchange brought about reversible σ-bond activation within alkyl C(sp3)–H bond; non-dissociative mechanism implied...

The two-coordinate ring-expanded N-heterocyclic carbene copper(I) complexes [Cu(RE-NHC)2]+ (RE-NHC = 6-Mes, 7-o-Tol, 7-Mes) have been prepared and shown to be effective catalysts under neat conditions for the 1,3-dipolar cycloaddition of alkynes azides. In contrast, cationic diamidocarbene analogue [Cu(6-MesDAC)2]+ neutral species [(6-MesDAC)CuCl]2 [(6-MesDAC)2(CuCl)3] show good activity when catalysis is performed on water.

Systems of the type [(p-cym)Ru(PR3)(H)(H2BNiPr2)]+ (R = Cy, Ph) can be synthesized from (p-cym)Ru(PR3)Cl2 and H2BNiPr2/Na[BArf4] are best formulated as (hydrido)ruthenium κ1-aminoborane complexes. VT-NMR measurements have been used to probe σ-bond metathesis process leading Ru–H/H–B exchange, yielding an activation barrier ΔG⧧ 7.5 kcal mol–1 at 161 K. Moreover, in contrast case for related non-hydride-containing systems, reactivity toward alkenes constitutes a viable route metal borylene...

Halide abstraction from the ruthenium N-heterocyclic carbene complex Ru(IPr)2(CO)HCl (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with NaBAr4F (BAr4F B{C6H3(3,5-CF3)2}4) gave salt [Ru(IPr)2(CO)H]BAr4F (2), which was shown through a combined X-ray/neutron structure refinement and quantum theory of atoms in molecules (QTAIM) study to contain bifurcated Ru···η3-H2C ξ-agostic interaction involving one iPr substituent IPr ligand. This system complements previously reported...

Abstract The hydride complex [Ru(IPr) 2 (CO)H][BAr F 4 ], 1 , reacts with InMe 3 loss of CH to form (CO)(InMe)(Me)][BAr featuring an unsupported Ru−In bond unsaturated Ru and In centres. H give (CO)(η ‐H )(InMe)(H)][BAr 5 while CO induces formation the indyl (CO) (InMe )][BAr 7 . These observations highlight ability Me shuttle between centres are supported by DFT calculations on mechanism its reactions CO. An analysis Ru‐In bonding in these species is also presented. Reaction GaMe involves...

Multiple catalytic hydrodefluorination steps take place with the<italic>trans</italic>-dihydride complex [Ru(IEt₂Me₂)₂(PPh₃)₂H₂] (<bold>1</bold>), taking C₆F₆to tri-, di- and mono-fluorobenzenes.

The ruthenium-zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF)ZnMe][BArF4] (12) and [Ru(IMes)'(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO)(η2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss coordinated dihydrogen ligand upon...

A metal templated synthetic approach gives access to [Cp*Fe(CO)(2){B(NMesCMe)(2)CH}][BAr(f)(4)], and represents the first example of coordinative trapping elusive [B(NRCMe)(2)CH] fragment.

α versus γ: [CpFe(CO)(PCy3)(BNCMes2)]+, synthesized by halide abstraction, represents the first example of a BN allenylidene analogue, and features an unsaturated MBNC π system. Although DFT calculations show significant LUMO amplitude at γ (carbon) position, primary reactivity towards nucleophiles occurs sterically less hindered (boron) center. Detailed facts importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or...

The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM=B=N=CR2](+), which feature a unique heterocumulene structure, have been systematically investigated. Precursors the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) generated by B-centred substitution chemistry using CpFe(CO)2BCl2 suitable lithiated ketimines - is found to be highly sensitive steric bulk at both metal fragment ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed halide...