[Ni(NHC)2 ] as a Scaffold for Structurally Characterized trans [H-Ni-PR2 ] and trans [R2 P-Ni-PR2 ] Complexes.

The addition of PPh2 H, PPhMeH, PPhH2 , P(para-Tol)H2 , PMesH2 and PH3 to the two-coordinate Ni0 N-heterocyclic carbene species [Ni(NHC)2 ] (NHC=IiPr2 , IMe4 , IEt2 Me2 ) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these compounds shows that they have unusual trans [H-Ni-PR2 ] or novel trans [R2 P-Ni-PR2 ] geometries. The bis-phosphido complexes are more accessible when smaller NHCs (IMe4 >IEt2 Me2 >IiPr2 ) and phosphines are employed. P-P activation of the diphosphines R2 P-PR2 (R2 =Ph2 , PhMe) provides an alternative route to some of the [Ni(NHC)2 (PR2 )2 ] complexes. DFT calculations capture these trends with P-H bond activation proceeding from unconventional phosphine adducts in which the H substituent bridges the Ni-P bond. P-P bond activation from [Ni(NHC)2 (Ph2 P-PPh2 )] adducts proceeds with computed barriers below 10 kcal mol-1 . The ability of the [Ni(NHC)2 ] moiety to afford isolable terminal phosphido products reflects the stability of the Ni-NHC bond that prevents ligand dissociation and onward reaction.

Mono- and dinuclear Ni(i) products formed upon bromide abstraction from the Ni(i) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br].

Bromide abstraction from the three-coordinate Ni(i) ring-expanded N-heterocyclic carbene complex [Ni(6-Mes)(PPh3)Br] (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) with TlPF6 in THF yields the T-shaped cationic solvent complex, [Ni(6-Mes)(PPh3)(THF)][PF6] (2), whereas treatment with NaBArF4 in Et2O affords the dimeric Ni(i) product, [{Ni(6-Mes)(PPh3)}2(µ-Br)][BArF4] (3). Both 2 and 3 act as latent sources of the cation [Ni(6-Mes)(PPh3)]+, which can be trapped by CO to give [Ni(6-Mes)(PPh3)(CO)]+ (5). Addition of [(Et3Si)2(µ-H)][B(C6F5)4] to 1 followed by work up in toluene results in the elimination of phosphine as well as halide to afford a co-crystallised mixture of [Ni(6-Mes)(η2-C6H5Me)][B(C6F5)4] (4), and [6MesHC6H5Me][B(C6F5)4]. Treatment of 1 with sodium salts of more strongly coordinating anions leads to substitution products. Thus, NaBH4 yields the neutral, diamagnetic dimer [{Ni(6-Mes)}2(BH4)2] (6), whereas NaBH3(CN) gives the paramagnetic monomeric cyanotrihydroborate complex [Ni(6-Mes)(PPh3)(NCBH3)] (7). Treatment of 1 with NaOtBu/NHPh2 affords the three-coordinate Ni(i) amido species, [Ni(6-Mes)(PPh3)(NPh2)] (8). The electronic structures of 2, 5, 7 and 8 have been analysed in comparison to that of previously reported 1 using a combination of EPR spectroscopy and density functional theory.

In situ decoration of graphene sheets with gold nanoparticles synthetized by pulsed laser ablation in liquids.

The demand for nanocomposites of graphene and carbonaceous materials decorated with metallic nanoparticles is increasing on account of their applications in science and technology. Traditionally, the production of graphene-metal assemblies is achieved by the non-environmentally friendly reduction of metallic salts in carbonaceous suspensions. However, precursor residues during nanoparticle growth may reduce their surface activity and promote cross-chemical undesired effects. In this work we present a laser-based alternative to synthesize ligand-free gold nanoparticles that are anchored onto the graphene surface in a single reaction step. Laser radiation is used to generate highly pure nanoparticles from a gold disk surrounded by a graphene oxide suspension. The produced gold nanoparticles are directly immobilized onto the graphene surface. Moreover, the presence of graphene oxide influences the size of the nanoparticles and its interaction with the laser, causes only a slight reduction of the material. This work constitutes a green alternative synthesis of graphene-metal assemblies and a practical methodology that may inspire future developments.

Hydrodefluorination of carbon-fluorine bonds by the synergistic action of a ruthenium-palladium catalyst.

Catalytic hydrodefluorination of organic molecules is a major organometallic challenge, owing to the strength of C-F sigma bonds, and it is a process with multiple industrial applications. Here we report a new heterodimetallic ruthenium-palladium complex based on a triazolyl-di-ylidene ligand. The complex is remarkably active in the hydrodefluorination of aromatic and aliphatic carbon-fluorine bonds under mild reaction conditions. We observe that both metals are required to promote the reaction process. The overall process implies that the palladium fragment facilitates the C-F activation, whereas the ruthenium centre allows the reduction of the substrate via transfer hydrogenation from isopropanol/sodium t-butoxide. The activity of this heterodimetallic complex is higher than that shown by a mixture of the related homodimetallic complexes of ruthenium and palladium, demonstrating the catalytic benefits of the heterodimetallic complex linked by a single-frame ligand.

Dual catalysis with an Ir(III)-Au(I) heterodimetallic complex: reduction of nitroarenes by transfer hydrogenation using primary alcohols.

A triazolyl-di-ylidene ligand has been used for the preparation of a homodimetallic complex of gold, and a heterodimetallic compound of gold and iridium. Both complexes have been fully characterized and their molecular structures have been determined by means of X-ray diffraction. The catalytic properties of these two complexes have been evaluated in the reduction of nitroarenes by transfer hydrogenation using primary alcohols. The two complexes afford different reaction products; whereas the Au(I)-Au(I) catalyst yields a hydroxylamine, the Ir(III)-Au(I) complex facilitates the formation of an imine.