Carbon–Carbon Bond Forming Reactions Promoted by Aluminyl and Alumoxane Anions: Introducing the Ethenetetraolate Ligand

[K{Al(NON^Dipp)}]₂ (NON^Dipp=[O(SiMe₂NDipp)₂]^2?, Dipp=2,6‐iPr₂C₆H₃) reacts with CS₂ to afford the trithiocarbonate species [K(OEt₂)][Al(NON^Dipp)(CS₃)] 1 or the ethenetetrathiolate complex, [K{Al(NON^Dipp)(S₂C)}]₂ [ 3 ]₂. The dimeric alumoxane [K{Al(NON^Dipp)(O)}]₂ reacts with carbon monoxide to afford the oxygen analogue of 3 , [K{Al(NON^Dipp)(O₂C)}]₂ [ 4 ]₂ containing the hitherto unknown ethenetetraolate ligand, [C₂O₄]^4?.     

Carbon–Carbon Bond Forming Reactions Promoted by Aluminyl and Alumoxane Anions: Introducing the Ethenetetraolate Ligand

[K{Al(NON^Dipp)}]₂ (NON^Dipp=[O(SiMe₂NDipp)₂]²⁻, Dipp=2,6-iPr₂C₆H₃) reacts with CS₂ to afford the trithiocarbonate species [K(OEt₂)][Al(NON^Dipp)(CS₃)] 1 or the ethenetetrathiolate complex, [K{Al(NON^Dipp)(S₂C)}]₂ [ 3 ]₂. The dimeric alumoxane [K{Al(NON^Dipp)(O)}]₂ reacts with carbon monoxide to afford the oxygen analogue of 3 , [K{Al(NON^Dipp)(O₂C)}]₂ [ 4 ]₂ containing the hitherto unknown ethenetetraolate ligand, [C₂O₄]⁴⁻.     

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

The deoxygenative conversion of carbon dioxide to carbon monoxide is promoted by the aluminyl anion [Al(NON^Ar)]^? (NON^Ar=[O(SiMe₂NAr)₂]^2?, Ar=2,6‐iPr₂C₆H₃). The reaction proceeds via the isolable monoalumoxane anion [Al(NON^Ar)(O)]^?, containing a terminal aluminum‐oxygen bond. This species reacts with a second equivalent of carbon dioxide to afford the carbonate [Al(NON^Ar)(CO₃)]^?, and with nitrous oxide to generate the hyponitrite anion, [Al(NON^Ar)(κ²O,O′‐N₂O₂)]^?.     

Uncovering selective and active Ga surface sites in gallia–alumina mixed-oxide propane dehydrogenation catalysts by dynamic nuclear polarization surface enhanced NMR spectroscopy

Gallia–alumina (Ga,Al)₂O_3(x : y) spinel-type solid solution nanoparticle catalysts for propane dehydrogenation (PDH) were prepared with four nominal Ga : Al atomic ratios (1 : 6, 1 : 3, 3 : 1, 1 : 0) using a colloidal synthesis approach. The structure, coordination environment and distribution of Ga and Al sites in these materials were investigated by X-ray diffraction, X-ray absorption spectroscopy (Ga K-edge) as well as ²⁷Al and ⁷¹Ga solid state nuclear magnetic resonance. The surface acidity (Lewis or Brønsted) was probed using infrared spectroscopy with pyridine and 2,6-dimethylpyridine probe molecules, complemented by element-specific insights (Ga or Al) from dynamic nuclear polarization surface enhanced cross-polarization magic angle spinning ¹⁵N{²⁷Al} and ¹⁵N{⁷¹Ga} J coupling mediated heteronuclear multiple quantum correlation NMR experiments using ¹⁵N-labelled pyridine as a probe molecule. The latter approach provides unique insights into the nature and relative strength of the surface acid sites as it allows to distinguish contributions from Al and Ga sites to the overall surface acidity of mixed (Ga,Al)₂O₃ oxides. Notably, we demonstrate that (Ga,Al)₂O₃ catalysts with a high Al content show a greater relative abundance of four-coordinated Ga sites and a greater relative fraction of weak/medium Ga-based surface Lewis acid sites, which correlates with superior propene selectivity, Ga-based activity, and stability in PDH (due to lower coking). In contrast, (Ga,Al)₂O₃ catalysts with a lower Al content feature a higher fraction of six-coordinated Ga sites, as well as more abundant Ga-based strong surface Lewis acid sites, which deactivate through coking. Overall, the results show that the relative abundance and strength of Ga-based surface Lewis acid sites can be tuned by optimizing the bulk Ga : Al atomic ratio, thus providing an effective measure for a rational control of the catalyst performance.

Coordination geometry and Lewis acidity of Ga and Al (bulk and surface) sites in mixed oxide gallia–alumina nanoparticles is correlated with the performance in propane dehydrogenation.     

Substituted aromatic pentaphosphole ligands – a journey across the p-block

The functionalization of pentaphosphaferrocene [Cp*Fe(η⁵-P₅)] (1) with cationic group 13–17 electrophiles is shown to be a general synthetic strategy towards P–E bond formation of unprecedented diversity. The products of these reactions are dinuclear [{Cp*Fe}₂{μ,η^5:5-(P₅)₂EX₂}][TEF] (EX₂ = BBr₂ (2), GaI₂ (3), [TEF]⁻ = [Al{OC(CF₃)₃}₄]⁻) or mononuclear [Cp*Fe(η⁵-P₅E)][X] (E = CH₂Ph (4), CHPh₂ (5), SiHPh₂ (6), AsCy₂ (7), SePh (9), TeMes (10), Cl (11), Br (12), I (13)) complexes of hetero-bis-pentaphosphole ((cyclo-P₅)₂R) or hetero-pentaphosphole ligands (cyclo-P₅R), the aromatic all-phosphorus analogs of prototypical cyclopentadienes. Further, modifying the steric and electronic properties of the electrophile has a drastic impact on its reactivity and leads to the formation of [Cp*Fe(μ,η^5:2-P₅)SbICp′′′][TEF] (8) which possesses a triple-decker-like structure. X-ray crystallographic characterization reveals the slightly twisted conformation of the cyclo-P₅R ligands in these compounds and multinuclear NMR spectroscopy confirms their integrity in solution. DFT calculations shed light on the bonding situation of these compounds and confirm the aromatic character of the pentaphosphole ligands on a journey across the p-block.

The reactivity of cationic electrophiles towards pentaphosphaferrocene [Cp*Fe(ƞ⁵-P₅)] is explored. We report P–E bond formation for electrophiles across the p-block, producing coordination complexes with unprecedented hetero-bispentaphosphole and hetero-pentaphosphole ligands.     

Kinetics of the uninhibited and ethanol-inhibited CoO,Co<Subscript>2</Subscript>O<Subscript>3</Subscript> and Ni<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyzed autoxidation of sulfur(IV) in alkaline medium

For getting an insight into the mechanism of atmospheric autoxidation of sulfur(IV), the kinetics of this autoxidation reaction catalyzed by CoO, Co₂O₃ and Ni₂O₃ in buffered alkaline medium has been studied, and found to be defined by Eqs. I and II for catalysis by cobalt oxides and Ni₂O₃, respectively.

Square-Planar Nickel(II) O,O′-Dialkyldithiophosphato Complexes with Triphenylphosphine of the Type [NiX(S2P{OR}2)(PPh3)] (X = Cl,Br, I and NCS)

A series of new [NiX(S₂P{O-c-Hex}₂)(PPh₃)](X = Cl^–, Br^–, I^– and NCS^–)(1)–(4) and [Ni(NCS)(S₂P{OR}₂)(PPh₃)][R =n-Pr (5), i-Pr (6)] complexes has been synthesized and characterized by elemental analyses, f.i.r., i.r., u.v.–vis., ¹H-, ¹³C{¹H}- and ³¹P{¹H}-n.m.r. spectra, magnetochemical and conductivity measurements. A single crystal X-ray analysis of [Ni(NCS)(S₂P{O-n-Pr}₂)(PPh₃)](5) reveals the molecular structure of the complex and confirms a square-planar geometry around the central atom of nickel with the NCS anion coordinated via the nitrogen atom.     

One Electron Makes Differences: From Heme {FeNO}7 to {FeNO}8

The first X‐ray single‐crystal structure of a {FeNO}⁸ porphyrin complex [Co(Cp)₂][Fe(TFPPBr₈)(NO)], and the structure of the {FeNO}⁷ precursor [Fe(TFPPBr₈)(NO)] are determined at 100 K. The two complexes are also characterized by FTIR and UV/Vis spectroscopy. [Fe(TFPPBr₈)(NO)]^? shows distinct structural features in contrast to a nitrosyl iron(II) porphyrinate on the Fe? N? O^? moiety, which include a much more bent Fe? N? O^? angle (122.4(3)°), considerably longer Fe? NO^? (1.814(4)) and N? O^? (1.194(5) Å) bond distances. These and the about 180 cm^?1 downshift ν_N‐O stretch (1540 cm^?1) can be understood by the covalently bonding nature between the iron(II) and the NO^? ligand which possesses a two‐electron‐occupied π* orbital as a result of the reduction. The overall structural features of [Fe(TFPPBr₈)(NO)]^? and [Fe(TFPPBr₈)(NO)] suggest a low‐spin state of the iron(II) atom at 100 K.     

Migratory insertion of isocyanide into a ketenyl–tungsten bond as key step in cyclization reactions

Treatment of the side-on tungsten alkyne complex of ethinylethyl ether [Tp*W(CO)₂(η²-C,C′-HCCOCH₂CH₃)]⁺ {Tp* = hydridotris(3,4,5-trimethylpyrazolyl)borate} (2a) with n-Bu₄NI afforded the end-on ketenyl complex [Tp*W(CO)₂(κ¹-HCCO)] (4a). This formal 16 ve complex bearing the prototype of a ketenyl ligand is surprisingly stable and converts only under activation by UV light or heat to form a dinuclear complex [Tp*₂W₂(CO)₄(μ-CCH₂)] (6). The ketenyl ligand in complex 4a underwent a metal template controlled cyclization reaction upon addition of isocyanides. The oxametallacycles [Tp*W(CO)₂{κ²-C,O-C(NHXy)C(H)C(Nu)O}] {Nu = OMe (7), OEt (8), N(i-Pr)₂ (9), OH (10), O_1/2 (11)} were formed by coordination of Xy-NC (Xy = 2,6-dimethylphenyl) at 4a and subsequent migratory insertion (MI) into the W-ketenyl bond. The resulting intermediate is susceptible to addition reactions with protic nucleophiles. Compounds 2a-PF₆, 4a/b, and 7–11 were fully characterized including XRD analysis. The cyclization mechanism has been confirmed both experimentally and by DFT calculations. In cyclic voltammetry, complexes 7–9 are characterized by a reversible W(ii)/W(iii) redox process. The dinuclear complex 11 however shows two separated redox events. Based on cyclic voltammetry measurements with different conducting electrolytes and IR spectroelectrochemical (SEC) measurements the W(ii)/W(iii) mixed valent complex 11⁺ is assigned to class II in terms of the Robin-Day classification.

The prototype ketenyl ligand is bound end-on despite a formal 16 valence electron count at the metal. This situation opens a reaction pathway for a multicomponent cyclization centred on the migration of the ketenyl ligand.     

Indyllithium and the Indyl Anion [InL]−: Heavy Analogues of N‐Heterocyclic Carbenes

Reduction of the indate complex In(NON^Ar)(μ‐Cl)₂Li(OEt₂)₂ (NON^Ar=[O(SiMe₂NAr)₂]^2?; Ar=2,6‐iPr₂C₆H₃) with sodium generates the In^II diindane species [In(NON^Ar)]₂. Further reduction with a mixture of potassium and [2.2.2]crypt affords the In^I N‐heterocyclic indyl anion [In(NON^Ar)]^?, which crystallizes with a non‐contacted [K([2.2.2]crypt)]⁺ cation. The indyl anion can also be isolated as the indyllithium compound In(NON^Ar)(Li{THF}₃), which contains an In?Li bond. Density functional theory calculations show that the HOMO of the indyl anion is a metal‐centred lone pair, and preliminary reactivity studies confirm its nucleophilic behaviour.     

New orthopalladated complexes of phosphorus ylides: Crystal structure of [Pd{CH{P(C7H6)(p-tolyl)2}COCH3}Cl{P(p-tolyl)3}]

This work reports on the preparation of the complexes [PdCl₂(Y¹)₂], [PdCl₂(Y²)₂] (Y¹ = (p-tolyl)₃PCHCOCH₃ (1a); Y² = Ph₃PCHCO₂CH₂Ph (1b)), [Pd{CHP(C₇H₆)(p-tolyl)₂COCH₃}(μ-Cl)]₂ (2a), [Pd{CHP(C₆H₄)Ph₂CO₂CH₂Ph}(μ-Cl)]₂ (2b), [Pd{CH{P(C₇H₆)(p-tolyl)₂}COCH₃}Cl(L)] (L = PPh₃ (3a), P(p-tolyl)₃ (4a)) and [Pd{CH{P(C₆H₄)Ph₂}CO₂CH₂Ph}Cl(L)] (L = PPh₃ (3b), P(p-tolyl)₃ (4b)). Orthometallation and ylide C-coordination in complexes 2a–4b are demonstrated by an X-ray diffraction study of 4a.     

Between imide,imidyl and nitrene – an imido iron complex in two oxidation states

Imidyl and nitrene metal species play an important role in the N-functionalisation of unreactive C–H bonds as well as the aziridination of olefines. We report on the synthesis of the trigonal imido iron complexes [Fe(NMes)L₂]^0,− (L = –N{Dipp}SiMe₃); Dipp = 2,6-diisopropyl-phenyl; Mes = (2,4,6-trimethylphenyl) via reaction of mesityl azide (MesN₃) with the linear iron precursors [FeL₂]^0,−. UV-vis-, EPR-, ⁵⁷Fe Mössbauer spectroscopy, magnetometry, and computational methods suggest for the reduced form an electronic structure as a ferromagnetically coupled iron(ii) imidyl radical, whereas oxidation leads to mixed iron(iii) imidyl and electrophilic iron(ii) nitrene character. Reactivity studies show that both complexes are capable of H atom abstraction from C–H bonds. Further, the reduced form [Fe(NMes)L₂]⁻ reacts nucleophilically with CS₂ by inserting into the imido iron bond, as well as electrophilically with CO under nitrene transfer. The neutral [Fe(NMes)L₂] complex shows enhanced electrophilic behavior as evidenced by nitrene transfer to a phosphine, yet in combination with an overall reduced reactivity.

A pair of trigonal imido iron complexes ([Fe(NMes)L₂]^0,−) in two oxidation states is reported. The anionic complex K{crypt.222}[Fe(NMes)L₂] is best described as an iron(ii) imide.     

Preparation and electrochemical properties of {\hbox{N}}{{\hbox{d}}_{{{2} - x}}}{\hbox{S}}{{\hbox{r}}_x}{\hbox{Fe}}{{\hbox{O}}_{{{4} + \delta }}} cathode materials for intermediate-temperature solid oxide fuel cells

Cathodic materials $ {\hbox{N}}{{\hbox{d}}_{{{2} - x}}}{\hbox{S}}{{\hbox{r}}_x}{\hbox{Fe}}{{\hbox{O}}_{{{4} + \delta }}} $ (x?=?0.5, 0.6, 0.8, 1.0) with K₂NiF₄-type structure, for use in intermediate-temperature solid oxide fuel cells (IT-SOFCs), have been prepared by the glycine?Cnitrate process and characterized by XRD, SEM, AC impedance spectroscopy, and DC polarization measurements. The results have shown that no reaction occurs between an $ {\hbox{N}}{{\hbox{d}}_{{{2} - x}}}{\hbox{S}}{{\hbox{r}}_x}{\hbox{Fe}}{{\hbox{O}}_{{{4} + \delta }}} $ electrode and an Sm_0.2Gd_0.8O_1.9 electrolyte at 1,200?°C, and that the electrode forms a good contact with the electrolyte after sintering at 1,000?°C for 2?h. In the series $ {\hbox{N}}{{\hbox{d}}_{{{2} - x}}}{\hbox{S}}{{\hbox{r}}_x}{\hbox{Fe}}{{\hbox{O}}_{{{4} + \delta }}} $ (x?=?0.5, 0.6, 0.8, 1.0), the composition $ {\hbox{N}}{{\hbox{d}}_{{{1}.0}}}{\hbox{S}}{{\hbox{r}}_{{{1}.0}}}{\hbox{Fe}}{{\hbox{O}}_{{{4} + \delta }}} $ shows the lowest polarization resistance and cathodic overpotential, 2.75????cm² at 700?°C and 68?mV at a current density of 24.3?mA?cm^?2 at 700?°C, respectively. It has also been found that the electrochemical properties are remarkably improved the increasing Sr content in the experimental range.     

Carbon dioxide reduction by an Al–O–P frustrated Lewis pair

The reaction of tBu₂P(O)H with Bis₂AlH (Bis = CH(SiMe₃)₂) afforded the adduct tBu₂P(H)–O–Al(H)Bis₂ (3). It slowly releases H₂ to form the first oxygen-bridged geminal Al/P frustrated Lewis pair tBu₂P–O–AlBis₂. It is capable of reversibly binding molecular hydrogen to afford 3, shown by NMR and H/D scrambling experiments, and forms a 1,2-adduct with CO₂. Importantly, the H₂ adduct 3 reduces CO₂ in a stoichiometric reaction leading to the formic acid adduct tBu₂P(H)–O–Al(CO₂H)Bis₂. The formation of the different species was explored by density functional theory calculations which provide support for the experimental results. All products were characterized by NMR spectroscopy as well as X-ray diffraction experiments and elemental analyses.

Addition vs. reduction: the geminal FLP Bis₂Al–O–PtBu₂ can reversibly bind molecular hydrogen, it reacts with CO₂ to give an adduct, and its hydrogen adduct reduces CO₂ to an adduct of formic acid.     

Modelling local structural and electronic consequences of proton and hydrogen-atom uptake in VO2 with polyoxovanadate clusters

We report the synthesis and characterisation of a series of siloxide-functionalised polyoxovanadate–alkoxide (POV–alkoxide) clusters, [V₆O₆(OSiMe₃)(OMe)₁₂]ⁿ (n = 1−, 2−), that serve as molecular models for proton and hydrogen-atom uptake in vanadium dioxide, respectively. Installation of a siloxide moiety on the surface of the Lindqvist core was accomplished via addition of trimethylsilyl trifluoromethylsulfonate to the fully-oxygenated cluster [V₆O₇(OMe)₁₂]²⁻. Characterisation of [V₆O₆(OSiMe₃)(OMe)₁₂]¹⁻ by X-ray photoelectron spectroscopy reveals that the incorporation of the siloxide group does not result in charge separation within the hexavanadate assembly, an observation that contrasts directly with the behavior of clusters bearing substitutional dopants. The reduced assembly, [V₆O₆(OSiMe₃)(OMe)₁₂]²⁻, provides an isoelectronic model for H-doped VO₂, with a vanadium(iii) ion embedded within the cluster core. Notably, structural analysis of [V₆O₆(OSiMe₃)(OMe)₁₂]²⁻ reveals bond perturbations at the siloxide-functionalised vanadium centre that resemble those invoked upon H-atom uptake in VO₂ through ab initio calculations. Our results offer atomically precise insight into the local structural and electronic consequences of the installation of hydrogen-atom-like dopants in VO₂, and challenge current perspectives of the operative mechanism of electron–proton co-doping in these materials.

We report the synthesis and characterisation of a series of siloxide-functionalised polyoxovanadate–alkoxide clusters, [V₆O₆(OSiMe₃)(OMe)₁₂]ⁿ (n = 1⁻, 2⁻), that serve as molecular models for proton and hydrogen-atom uptake in vanadium dioxide.     

Density functional theory study of the structures and stabilities of CuO\documentclass{article}\pagestyle{empty}\begin{document}$_{3}^{-}$\end{document} and CuO3

Hybrid density functional theory calculations on the structures, vibrational frequencies, electron binding and dissociation energies, and bonding properties of CuO$_{3}^{-}$ and CuO₃ species have been carried out. Stable isomers containing an O₃ subunit and composed of O₂ bound to CuO have been located on the potential energy hypersurfaces of CuO$_{3}^{-}$ and CuO₃. The isomers formed by O₂ bonded to CuO in side‐on and end‐on coordination are more stable than those containing an O₃ subunit. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 81: 162–168, 2001     

Cooperative B–H bond activation: dual site borane activation by redox active κ2-N,S-chelated complexes

Cooperative dual site activation of boranes by redox-active 1,3-N,S-chelated ruthenium species, mer-[PR₃{κ²-N,S-(L)}₂Ru{κ¹-S-(L)}], (mer-2a: R = Cy, mer-2b: R = Ph; L = NC₇H₄S₂), generated from the aerial oxidation of borate complexes, [PR₃{κ²-N,S-(L)}Ru{κ³-H,S,S′-BH₂(L)₂}] (trans–mer-1a: R = Cy, trans–mer-1b: R = Ph; L = NC₇H₄S₂), has been investigated. Utilizing the rich electronic behaviour of these 1,3-N,S-chelated ruthenium species, we have established that a combination of redox-active ligands and metal–ligand cooperativity has a big influence on the multisite borane activation. For example, treatment of mer-2a–b with BH₃·THF led to the isolation of fac-[PR₃Ru{κ³-H,S,S′-(NH₂BSBH₂N)(S₂C₇H₄)₂}] (fac-3a: R = Cy and fac-3b: R = Ph) that captured boranes at both sites of the κ²-N,S-chelated ruthenacycles. The core structure of fac-3a and fac-3b consists of two five-membered ruthenacycles [RuBNCS] which are fused by one butterfly moiety [RuB₂S]. Analogous fac-3c, [PPh₃Ru{κ³-H,S,S′-(NH₂BSBH₂N)(SC₅H₄)₂}], can also be synthesized from the reaction of BH₃·THF with [PPh₃{κ²-N,S-(SNC₅H₄)}{κ³-H,S,S′-BH₂(SNH₄C₅)₂}Ru], cis–fac-1c. In stark contrast, when mer-2b was treated with BH₂Mes (Mes = 2,4,6-trimethyl phenyl) it led to the formation of trans- and cis-bis(dihydroborate) complexes [{κ³-S,H,H-(NH₂BMes)Ru(S₂C₇H₄)}₂], (trans-4 and cis-4). Both the complexes have two five-membered [Ru–(H)₂–B–NCS] ruthenacycles with κ²-H–H coordination modes. Density functional theory (DFT) calculations suggest that the activation of boranes across the dual Ru–N site is more facile than the Ru–S one.

Redox-active ruthenium complexes supported by hemilabile κ²-N,S-chelated ruthenacycles undergo unusual dual site B–H bond activation through metal–ligand cooperation with free and bulky boranes.     

Reversible carbon–boron bond formation at platinum centers through σ-BH complexes

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(ii) complex [Pt(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F], 1, with tricoordinated boranes HBR₂. X-ray diffraction studies provided structural snapshots of the sequence of reactions involved in the process. At low temperature, we observed the initial formation of the unprecedented σ-BH complexes [Pt(HBR₂)(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F], one of which has been isolated. From −15 to +10 °C, the σ-BH species undergo a carbon–boron coupling process leading to the platinum hydride derivative [Pt(H)(I^tBuⁱPr–BR₂)(I^tBuⁱPr)][BAr^F], 4. Surprisingly, these compounds are thermally unstable undergoing carbon–boron bond cleavage at room temperature that results in the 14-electron Pt(ii) boryl species [Pt(BR₂)(I^tBuⁱPr)₂][BAr^F], 2. This unusual reaction process has been corroborated by computational methods, which indicate that the carbon–boron coupling products 4 are formed under kinetic control whereas the platinum boryl species 2, arising from competitive C–H bond coupling, are thermodynamically more stable. These findings provide valuable information about the factors governing productive carbon–boron coupling reactions at transition metal centers.

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(ii) complex [Pt(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F], 1, with tricoordinated boranes HBR₂.     

Ni(0)-promoted activation of Csp2–H and Csp2–O bonds

A dinickel(0)–N₂ complex, stabilized with a rigid acridane-based PNP pincer ligand, was studied for its ability to activate C(sp²)–H and C(sp²)–O bonds. Stabilized by a Ni–μ–N₂–Na⁺ interaction, it activates C–H bonds of unfunctionalized arenes, affording nickel–aryl and nickel–hydride products. Concomitantly, two sodium cations get reduced to Na(0), which was identified and quantified by several methods. Our experimental results, including product analysis and kinetic measurements, strongly suggest that this C(sp²)–H activation does not follow the typical oxidative addition mechanism occurring at a low-valent single metal centre. Instead, via a bimolecular pathway, two powerfully reducing nickel ions cooperatively activate an arene C–H bond and concomitantly reduce two Lewis acidic alkali metals under ambient conditions. As a novel synthetic protocol, nickel(ii)–aryl species were directly synthesized from nickel(ii) precursors in benzene or toluene with excess Na under ambient conditions. Furthermore, when the dinickel(0)–N₂ complex is accessed via reduction of the nickel(ii)–phenyl species, the resulting phenyl anion deprotonates a C–H bond of glyme or 15-crown-5 leading to C–O bond cleavage, which produces vinyl ether. The dinickel(0)–N₂ species then cleaves the C(sp²)–O bond of vinyl ether to produce a nickel(ii)–vinyl complex. These results may provide a new strategy for the activation of C–H and C–O bonds mediated by a low valent nickel ion supported by a structurally rigidified ligand scaffold.

A structurally rigidified nickel(0) complex was found to be capable of cleaving both C(sp²)–H and C(sp²)–O bonds.     

Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform

A stepwise build-up of multi-substituted C_sp³ carbon centers is an attractive, conceptually simple, but often synthetically challenging type of disconnection. To this end, this report describes how gem-α,α-dimetalloid-substituted benzylic reagents bearing boron/silicon or boron/tin substituent sets are an excellent stepping stone towards diverse substitution patterns. These gem-dimetalloids were readily accessed, either by known carbenoid insertion into C–B bonds or by the newly developed scalable deprotonation/metallation approach. Highly chemoselective transformations of either the C–Si (or C–Sn) or the C–B bonds in the newly formed gem-C_sp³ centers have been achieved through a set of approaches, with a particular focus on exploiting the synthetically versatile polarity reversal in organometalloids by λ³-aryliodanes. Of particular note is the metal-free arylation of the C–Si (or C–Sn) bonds in such gem-dimetalloids via the iodane-guided C–H coupling approach. DFT calculations show that this transfer of the (α-Bpin)benzyl group proceeds via unusual [5,5]-sigmatropic rearrangement and is driven by the high-energy iodine(iii) center. As a complementary tool, the gem-dimetalloid C–B bond is shown to undergo a potent and chemoselective Suzuki–Miyaura arylation with diverse Ar–Cl, thanks to the development of the reactive gem-α,α-silyl/BF₃K building blocks.

This work explores divergent reactivity of the benzylic gem-boron–silicon and boron–tin double nucleophiles, including the arylation of the C–B bond with Ar–Cl, along with a complementary oxidative λ³-iodane-guided arylation of the C–Si/Sn moiety.