Metathetical Exchange between Metal-Metal Triple Bonds.

The reaction of the molybdenum-molybdenum triple-bonded dimer (CO)2CpMo≡MoCp(CO)2 (Cp = η5-C5H5) with the triple-bonded dimetallynes AriPr4MMAriPr4 or AriPr6MMAriPr6 (AriPr4 = C6H3-2,6-(C6H3-2,6-Pri2)2, AriPr6 = C6H3-2,6-(C6H2-2,4,6-Pri3)2; M = Ge, Sn, or Pb) under mild conditions (≤80 °C, 1 bar) afforded AriPr4M≡MoCp(CO)2 or AriPr6M≡MoCp(CO)2 in moderate to excellent yields. The reactions represent the first isolable products from a metathesis of two metal-metal triple bonds. Analogous exchange reactions with the single-bonded (CO)3CpMo-MoCp(CO)3 gave ArM̈-MoCp(CO)3 (Ar = AriPr4 or AriPr6; M = Sn or Pb). The products were characterized by NMR (1H, 13C, 119Sn, or 207Pb), electronic, and IR spectroscopy and by X-ray crystallography.

Highlights from Faraday Discussion: Artificial Photosynthesis, Cambridge, UK, March 2019.

This Faraday Discussion was held on March 25-27th, 2019 at Murray Edwards College, Cambridge, UK and was attended by 160 delegates from over 20 countries. The attendees represented the cross-disciplinary nature of the field, with biologists, engineers, material scientists, theoreticians and experimental chemists of all experience levels coming together to discuss the state of the art. The meeting captured how rapidly the field of artificial photosynthesis has progressed in a short time and highlighted how far we still have to go. In this conference report, the topics of discussion will be outlined with a brief description of the papers presented and a summary of the conference events.

Selective CO2 Reduction Catalyzed by Single Cobalt Sites on Carbon Nitride under Visible-Light Irradiation.

Framework nitrogen atoms of carbon nitride (C3N4) can coordinate with and activate metal sites for catalysis. In this study, C3N4 was employed to harvest visible light and activate Co2+ sites, without the use of additional ligands, in photochemical CO2 reduction. Photocatalysts containing single Co2+ sites on C3N4 were prepared by a simple deposition method and demonstrated excellent activity and product selectivity toward CO formation. A turnover number of more than 200 was obtained for CO production using the synthesized photocatalyst under visible-light irradiation. Inactive cobalt oxides formed at relatively high cobalt loadings but did not alter product selectivity. Further studies with X-ray absorption spectroscopy confirmed the presence of single Co2+ sites on C3N4 and their important role in achieving selective CO2 reduction.

Enhancing Light Absorption and Charge Transfer Efficiency in Carbon Dots through Graphitization and Core Nitrogen Doping.

Single-source precursor syntheses have been devised for the preparation of structurally similar graphitic carbon dots (CDs), with (g-N-CD) and without (g-CD) core nitrogen doping for artificial photosynthesis. An order of magnitude improvement has been realized in the rate of solar (AM1.5G) H2 evolution using g-N-CD (7950 µmolH2 (gCD )-1 h-1 ) compared to undoped CDs. All graphitized CDs show significantly enhanced light absorption compared to amorphous CDs (a-CD) yet undoped g-CD display limited photosensitizer ability due to low extraction of photogenerated charges. Transient absorption spectroscopy showed that nitrogen doping in g-N-CD increases the efficiency of hole scavenging by the electron donor and thereby significantly extends the lifetime of the photogenerated electrons. Thus, nitrogen doping allows the high absorption coefficient of graphitic CDs to be translated into high charge extraction for efficient photocatalysis.

Dynamic Behavior and Isomerization Equilibria of Distannenes Synthesized by Tin Hydride/Olefin Insertions: Characterization of the Elusive Monohydrido Bridged Isomer.

The tin(II) hydride [AriPr6Sn(µ-H)]2(AriPr6 = C6H3-2,6(C6H2-2,4,6-iPr3)2) (1a) reacts with 2 equiv of ethylene or t-butylethylene at ca. 25 °C to yield Sn2(AriPr6)2R2(R = ethyl or t-butylethyl), which exist either as a symmetric distannene AriPr6(R)SnSn(R)AriPr6 (2a or 5a) or an unsymmetric stannylstannylene AriPr6SnSnR2AriPr6 (3a). In contrast, the less crowded Sn(II) hydride [AriPr4Sn(µ-H)]2 (AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2) (1b) reacts with excess ethylene to give AriPr4(CH2CH3)2Sn(CH2CH2)Sn(CH2CH3)(CHCH2)AriPr4 (4) featuring five ethylene equivalents, one of which is dehydrogenated to an vinyl, -CH═CH2, group. The AriPr4 isomers of 2a and 3a, i.e., [AriPr4Sn(C2H5)]2 (2b) and AriPr4SnSn(C2H5)2AriPr4 (3b) are obtained by reaction of [AriPr4Sn(µ-Cl)]2 with EtLi or EtMgBr. The isomeric pairs 2a and 3a are separated by crystallization at different temperatures. Variable-temperature 1H NMR spectroscopy indicates fast ethyl group exchange between Ar(C2H5)SnSn(C2H5)Ar (Ar = AriPr6 (2a) or AriPr4 (2b)) and ArSnSn(C2H5)2Ar (Ar = AriPr6 (3a) or AriPr4 (3b)) with ΔG⧧ = 14.2 ± 0.65 kcal mol-1 for 2a/3a and 14.8 ± 0.36 kcal mol-1 for 2b/3b. The bulkier distannenes [ArSn(CH2CH2tBu)]2 (Ar = AriPr6 (5a) or AriPr4 (5b)), obtained from 1a or 1b and t-butylethylene, dissociate to ArSnCH2CH2tBu monomers in solution. At lower temperature, they interconvert with their stannylstannylene isomers with parameters Keq = 4.09 ± 0.16 for 5a and 6.38 ± 0.41 for 5b and ΔGeq = -1.81 ± 0.19 kcal mol-1 for 5a and -1.0 ± 0.03 kcal mol-1 for 5b at 298 K. The 1:1 reaction of 1a or 1b with 5a or 5b yields the unknown monohydrido species Sn2RHAr2 which has the structure AriPr6Sn-Sn(H)(CH2CH2tBu)AriPr6 (6a) or the monohydrido bridged AriPr4S n(µ-H)S n(CH2CH2tBu)AriPr4 (6b). The latter represents the first structural characterization of a monohydrido bridged isomer of a ditetrelene.

Tin(II) Hydrides as Intermediates in Rearrangements of Tin(II) Alkyl Derivatives.

Reactions of the Sn(II) hydrides [ArSn(µ-H)]2 (1) (Ar = AriPr4 (1a), AriPr6 (1b); AriP4 = C6H3-2,6-(C6H3-2,6-iPr2)2, AriPr6 = C6H3-2,6-(C6H2-2,4,6-iPr3)2) with norbornene (NB) or norbornadiene (NBD) readily generate the bicyclic alkyl-/alkenyl-substituted stannylenes, ArSn(norbornyl) (2a or 2b) and ArSn(norbornenyl) (3a or 3b), respectively. Heating a toluene solution of 3a or 3b at reflux afforded the rearranged species ArSn(3-tricyclo[2.2.1.02,6]heptane) (4a or 4b), in which the norbornenyl ligand is transformed into a nortricyclyl group. 1H NMR studies of the reactions of 4a or 4b with tert-butylethylene indicated the existence of an apparently unique reversible ß-hydride elimination from the bicyclic substituted aryl/alkyl stannylenes 2a or 2b and 3a or 3b. Mechanistic studies indicated that the transformation of 3a or 3b into 4a or 4b occurs via a ß-hydride elimination of 1a or 1b to regenerate NBD. Kinetic studies showed that the conversion of 3a or 3b to 4a or 4b is first order. The rate constant k for the conversion of 3a into 3b was determined to be 3.33 × 10-5 min-1, with an activation energy Ea of 16.4 ± 0.7 kcal mol-1.

Carbon Dots as Versatile Photosensitizers for Solar-Driven Catalysis with Redox Enzymes.

Light-driven enzymatic catalysis is enabled by the productive coupling of a protein to a photosensitizer. Photosensitizers used in such hybrid systems are typically costly, toxic, and/or fragile, with limited chemical versatility. Carbon dots (CDs) are low-cost, nanosized light-harvesters that are attractive photosensitizers for biological systems as they are water-soluble, photostable, nontoxic, and their surface chemistry can be easily modified. We demonstrate here that CDs act as excellent light-absorbers in two semibiological photosynthetic systems utilizing either a fumarate reductase (FccA) for the solar-driven hydrogenation of fumarate to succinate or a hydrogenase (H2ase) for reduction of protons to H2. The tunable surface chemistry of the CDs was exploited to synthesize positively charged ammonium-terminated CDs (CD-NHMe2+), which were capable of transferring photoexcited electrons directly to the negatively charged enzymes with high efficiency and stability. Enzyme-based turnover numbers of 6000 mol succinate (mol FccA)-1 and 43,000 mol H2 (mol H2ase)-1 were reached after 24 h. Negatively charged carboxylate-terminated CDs (CD-CO2-) displayed little or no activity, and the electrostatic interactions at the CD-enzyme interface were determined to be essential to the high photocatalytic activity observed with CD-NHMe2+. The modular surface chemistry of CDs together with their photostability and aqueous solubility make CDs versatile photosensitizers for redox enzymes with great scope for their utilization in photobiocatalysis.

Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride-Molecular Ni Catalyst System.

Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride ((NCN)CNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The (NCN)CNx-NiP system showed an activity of 763 µmol (g CNx)(-1) h(-1) toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h(-1), and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of (NCN)CNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited (NCN)CNx in the presence of an organic substrate can accumulate ultralong-lived "trapped electrons", which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel.

Addition of alkynes to digermynes: experimental insight into the reaction pathway.

The addition of an alkynyl cyclopropyl mechanistic probe to a digermyne did not lead to any ring-opened rearrangement products indicating that the reaction pathway does not involve any vinylic radicals or cations and providing experimental insight into the addition of alkynes to digermynes.

[NiFeSe]-hydrogenase chemistry.

The development of technology for the inexpensive generation of the renewable energy vector H2 through water splitting is of immediate economic, ecological, and humanitarian interest. Recent interest in hydrogenases has been fueled by their exceptionally high catalytic rates for H2 production at a marginal overpotential, which is presently only matched by the nonscalable noble metal platinum. The mechanistic understanding of hydrogenase function guides the design of synthetic catalysts, and selection of a suitable hydrogenase enables direct applications in electro- and photocatalysis. [FeFe]-hydrogenases display excellent H2 evolution activity, but they are irreversibly damaged upon exposure to O2, which currently prevents their use in full water splitting systems. O2-tolerant [NiFe]-hydrogenases are known, but they are typically strongly biased toward H2 oxidation, while H2 production by [NiFe]-hydrogenases is often product (H2) inhibited. [NiFeSe]-hydrogenases are a subclass of [NiFe]-hydrogenases with a selenocysteine residue coordinated to the active site nickel center in place of a cysteine. They exhibit a combination of unique properties that are highly advantageous for applications in water splitting compared with other hydrogenases. They display a high H2 evolution rate with marginal inhibition by H2 and tolerance to O2. [NiFeSe]-hydrogenases are therefore one of the most active molecular H2 evolution catalysts applicable in water splitting. Herein, we summarize our recent progress in exploring the unique chemistry of [NiFeSe]-hydrogenases through biomimetic model chemistry and the chemistry with [NiFeSe]-hydrogenases in semiartificial photosynthetic systems. We gain perspective from the structural, spectroscopic, and electrochemical properties of the [NiFeSe]-hydrogenases and compare them with the chemistry of synthetic models of this hydrogenase active site. Our synthetic models give insight into the effects on the electronic properties and reactivity of the active site upon the introduction of selenium. We have utilized the exceptional properties of the [NiFeSe]-hydrogenase from Desulfomicrobium baculatum in a number of photocatalytic H2 production schemes, which are benchmark systems in terms of single site activity, tolerance toward O2, and in vitro water splitting with biological molecules. Each system comprises a light-harvesting component, which allows for light-driven electron transfer to the hydrogenase in order for it to catalyze H2 production. A system with [NiFeSe]-hydrogenase on a dye-sensitized TiO2 nanoparticle gives an enzyme-semiconductor hybrid for visible light-driven generation of H2 with an enzyme-based turnover frequency of 50 s(-1). A stable and inexpensive polymeric carbon nitride as a photosensitizer in combination with the [NiFeSe]-hydrogenase shows good activity for more than 2 days. Light-driven H2 evolution with the enzyme and an organic dye under high O2 levels demonstrates the excellent robustness and feasibility of water splitting with a hydrogenase-based scheme. This has led, most recently, to the development of a light-driven full water splitting system with a [NiFeSe]-hydrogenase wired to the water oxidation enzyme photosystem II in a photoelectrochemical cell. In contrast to the other systems, this photoelectrochemical system does not rely on a sacrificial electron donor and allowed us to establish the long sought after light-driven water splitting with an isolated hydrogenase.

Solar hydrogen production using carbon quantum dots and a molecular nickel catalyst.

Carbon quantum dots (CQDs) are established as excellent photosensitizers in combination with a molecular catalyst for solar light driven hydrogen production in aqueous solution. The inexpensive CQDs can be prepared by straightforward thermolysis of citric acid in a simple one-pot, multigram synthesis and are therefore scalable. The CQDs produced reducing equivalents under solar irradiation in a homogeneous photocatalytic system with a Ni-bis(diphosphine) catalyst, giving an activity of 398 µmolH2 (gCQD)(-1) h(-1) and a "per Ni catalyst" turnover frequency of 41 h(-1). The CQDs displayed activity in the visible region beyond λ > 455 nm and maintained their full photocatalytic activity for at least 1 day under full solar spectrum irradiation. A high quantum efficiency of 1.4% was recorded for the noble- and toxic-metal free photocatalytic system. Thus, CQDs are shown to be a highly sustainable light-absorbing material for photocatalytic schemes, which are not limited by cost, toxicity, or lack of scalability. The photocatalytic hybrid system was limited by the lifetime of the molecular catalyst, and intriguingly, no photocatalytic activity was observed using the CQDs and 3d transition metal salts or platinum precursors. This observation highlights the advantage of using a molecular catalyst over commonly used heterogeneous catalysts in this photocatalytic system.

Carbon nitride-TiO2 hybrid modified with hydrogenase for visible light driven hydrogen production.

A system consisting of a [NiFeSe]-hydrogenase (H2ase) grafted on the surface of a TiO2 nanoparticle modified with polyheptazine carbon nitride polymer, melon (CN x ) is reported. This semi-biological assembly shows a turnover number (TON) of more than 5.8 × 105 mol H2 (mol H2ase)-1 after 72 h in a sacrificial electron donor solution at pH 6 during solar AM 1.5 G irradiation. An external quantum efficiency up to 4.8% for photon-to-hydrogen conversion was achieved under irradiation with monochromatic light. The CN x -TiO2-H2ase construct was also active under UV-free solar light irradiation (λ > 420 nm), where it showed a substantially higher activity than TiO2-H2ase and CN x -H2ase due, in part, to the formation of a CN x -TiO2 charge transfer complex and highly productive electron transfer to the H2ase. The CN x -TiO2-H2ase system sets a new benchmark for photocatalytic H2 production with a H2ase immobilised on a noble- and toxic-metal free light absorber in terms of visible light utilisation and stability.

Photocatalytic hydrogen production using polymeric carbon nitride with a hydrogenase and a bioinspired synthetic Ni catalyst.

Solar-light-driven H2 production in water with a [NiFeSe]-hydrogenase (H2ase) and a bioinspired synthetic nickel catalyst (NiP) in combination with a heptazine carbon nitride polymer, melon (CN(x)), is reported. The semibiological and purely synthetic systems show catalytic activity during solar light irradiation with turnover numbers (TONs) of more than 50,000 mol H2(mol H2ase)(-1) and approximately 155 mol H2 (mol NiP)(-1) in redox-mediator-free aqueous solution at pH 6 and 4.5, respectively. Both systems maintained a reduced photoactivity under UV-free solar light irradiation (λ>420 nm).

Photocatalytic Hydrogen Production using Polymeric Carbon Nitride with a Hydrogenase and a Bioinspired Synthetic Ni Catalyst.

Solar-light-driven H2 production in water with a [NiFeSe]-hydrogenase (H2ase) and a bioinspired synthetic nickel catalyst (NiP) in combination with a heptazine carbon nitride polymer, melon (CNx), is reported. The semibiological and purely synthetic systems show catalytic activity during solar light irradiation with turnover numbers (TONs) of more than 50 000 mol H2 (mol H2ase)-1 and approximately 155 mol H2 (mol NiP)-1 in redox-mediator-free aqueous solution at pH 6 and 4.5, respectively. Both systems maintained a reduced photoactivity under UV-free solar light irradiation (λ>420 nm).

Activation of gaseous PH3 with low coordinate diaryltetrylene compounds.

The reaction of phosphine gas with a low coordinate diaryl germylene or diarylstannylene results in both oxidative addition and arene elimination at the group 14 atom. The products were characterised by (31)P NMR spectroscopy and X-ray crystallography, and represent the first P-H bond activation by a heavy group 14 element compound.

Counterintuitive mechanisms of the addition of hydrogen and simple olefins to heavy group 13 alkene analogues.

The mechanism of the reaction of olefins and hydrogen with dimetallenes ArMMAr (Ar = aromatic group; M = Al or Ga) was studied by density functional theory calculations and experimental methods. The digallenes, for which the most experimental data are available, are extensively dissociated to gallanediyl monomers, :GaAr, in hydrocarbon solution, but the calculations and experimental data showed also that they react with simple olefins, such as ethylene, as intact ArGaGaAr dimers via stepwise [2 + 2 + 2] cycloadditions due to their considerably lower activation barriers vis-à-vis the gallanediyl monomers, :GaAr. This pathway was preferred over the [2 + 2] cycloaddition of olefin to monomeric :GaAr to form a gallacyclopropane ring with subsequent dimerization to yield the 1,2-digallacyclobutane intermediate and, subsequently, the 1,4-digallacyclohexane product. The calculations showed also that the addition of H(2) to digallene proceeds by a different mechanism involving the initial addition of one equivalent of H(2) to form a 1,2-dihydride intermediate. This reacts with a second equivalent of H(2) to give two ArGaH(2) fragments which recombine to give the observed product with terminal and bridging H-atoms, Ar(H)Ga(µ-H)(2)Ga(H)Ar. The computations agree with the experimental observation that the :GaAr(iPr(8)) (Ar(iPr(8)) = C(6)H-2,6-(C(6)H(3)-2,4,6-(i)Pr(3))(2)-3,5-(i)Pr(2)), which does not associate even in the solid state, does not react with ethylene or hydrogen. Calculations on the reaction of propene with ArAlAlAr show that, in contrast to the digallenes, addition involves an open-shell transition state consistent with the higher singlet diradical character of dialuminenes.

The role of group 14 element hydrides in the activation of C-H bonds in cyclic olefins.

Formally, triple-bonded dimetallynes ArEEAr [E = Ge (1), Sn (2); Ar = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2)] have been previously shown to activate aliphatic, allylic C-H bonds in cyclic olefins, cyclopentadiene (CpH), cyclopentene (c-C(5)H(8)) and 1,4-cyclohexadiene, with intriguing selectivity. In the case of the five-membered carbocycles, cyclopentadienyl species ArECp [E = Ge (3), Sn (4)] are formed. In this study, we examine the mechanisms for activation of CpH and c-C(5)H(8) using experimental methods and describe a new product found from the reaction between 1 and c-C(5)H(8), an asymmetrically substituted digermene ArGe(H)Ge(c-C(5)H(9))Ar (5), crystallized in 46% yield. This compound contains a hydrogenated cyclopentyl moiety and is found to be produced in a 3:2 ratio with 3, explaining the fate of the liberated H atoms following triple C-H activation. We show that when these C-H activation reactions are carried out in the presence of tert-butyl ethylene (excess), compounds {ArE(CH(2)CH(2)tBu)}(2) [E = Ge(8), Sn(9)] are obtained in addition to ArECp; in the case of CpH, the neohexyl complexes replace the production of H(2) gas, and for c-C(5)H(8) they displace cyclopentyl product 5 and account for all the hydrogen removed in the dehydroaromatization reactions. To confirm the source of 8 and 9, it was demonstrated that these molecules are formed cleanly between the reaction of (ArEH)(2) [E = Ge(6), Sn(7)] and tert-butyl ethylene, new examples of noncatalyzed hydro-germylation and -stannylation. Therefore, the presence of transient hydrides of the type 6 and 7 can be surmised to be reactive intermediates in the production of 3 and 4, along with H(2), from 1 and 2 and CpH (respectively), or the formation of 3 and 5 from 1. The reaction of 6 or 7 with CpH gave 3 or 4, respectively, with concomitant H(2) evolution, demonstrating the basic nature of these low-valent group 14 element hydrides and their key role in the 'cascade' of C-H activation steps. Additionally, during the course of these studies a new polycyclic compound (ArGe)(2)(C(7)H(12)) (10) was obtained in 60% yield from the reaction of 1,6-heptadiene and 1 via double [2 + 2] cycloaddition and gives evidence for a nonradical mechanism for these types of reactions.

Reversible and irreversible higher-order cycloaddition reactions of polyolefins with a multiple-bonded heavier group 13 alkene analogue: contrasting the behavior of systems with π-π, π-π*, and π-n+ frontier molecular orbital symmetry.

The heavier group 13 element alkene analogue, digallene Ar(iPr(4))GaGaAr(iPr(4)) (1) [Ar(iPr(4)) = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2)], has been shown to react readily in [n + 2] (n = 6, 4, 2 + 2) cycloaddition reactions with norbornadiene and quadricyclane, 1,3,5,7-cyclooctatetraene, 1,3-cyclopentadiene, and 1,3,5-cycloheptatriene to afford the heavier element deltacyclane species Ar(iPr(4))Ga(C(7)H(8))GaAr(iPr(4)) (2), pseudoinverse sandwiches Ar(iPr(4))Ga(C(8)H(8))GaAr(iPr(4)) (3, 3(iso)), and polycyclic compounds Ar(iPr(4))Ga(C(5)H(6))GaAr(iPr(4)) (4) and Ar(iPr(4))Ga(C(7)H(8))GaAr(iPr(4)) (5, 5(iso)), respectively, under ambient conditions. These reactions are facile and may be contrasted with other all-carbon versions, which require transition-metal catalysis or forcing conditions (temperature, pressure), or with the reactions of the corresponding heavier group 14 species Ar(iPr(4))EEAr(iPr(4)) (E = Ge, Sn), which give very different product structures. We discuss several mechanistic possibilities, including radical- and non-radical-mediated cyclization pathways. These mechanisms are consistent with the improved energetic accessibility of the LUMO of the heavier group 13 element multiple bond in comparison with that of a simple alkene or alkyne. We show that the calculated frontier molecular orbitals (FMOs) of Ar(iPr(4))GaGaAr(iPr(4)) are of π-π symmetry, allowing this molecule to engage in a wider range of reactions than permitted by the usual π-π* FMOs of C-C π bonds or the π-n(+) FMOs of heavier group 14 alkyne analogues.

Activation of olefins with low-valent gallium compounds under ambient conditions.

The reactions of Ar'GaGaAr' (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2)) with alkenes revealed the addition of two olefins per Ar'GaGaAr' under ambient conditions for ethylene, propene, 1-hexene and styrene but no reactions with more hindered or cyclic olefins.