Mechanistic Insights about the Ligand-Enabled Oxy-arylation/vinylation of Alkenes via Au(I)/Au(III) Catalysis.

The mechanism of oxy-arylation/vinylation of alkenes catalyzed by the (MeDalphos)AuCl complex was comprehensively investigated by DFT. (P,N)Au(Ph)2+ and (P,N)Au(vinyl)2+ are key intermediates accounting for the activation of the alkenols and for their cyclization by outer-sphere nucleophilic attack of oxygen. The 5-exo and 6-endo paths have been computed and compared, reproducing the peculiar regioselectivity difference observed experimentally between 4-penten-1-ol, (E) and (Z)-4-hexen-1-ols. Examining the way the alkenol coordinates to gold (more η2 or η1 ) can offer, in some cases, a simple way to predict the favored path of cyclization.

Evidence for genuine hydrogen bonding in gold(I) complexes.

The ability of gold to act as proton acceptor and participate in hydrogen bonding remains an open question. Here, we report the synthesis and characterization of cationic gold(I) complexes featuring ditopic phosphine-ammonium (P,NH+) ligands. In addition to the presence of short Au∙∙∙H contacts in the solid state, the presence of Au∙∙∙H-N hydrogen bonds was inferred by NMR and IR spectroscopies. The bonding situation was extensively analyzed computationally. All features were consistent with the presence of three-center four-electron attractive interactions combining electrostatic and orbital components. The role of relativistic effects was examined, and the analysis is extended to other recently described gold(I) complexes.

Gold(I) α-Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies.

Aryl trifluoromethyl diazomethanes 2-R (R=Ph, OMe, CF3 ) are readily decomposed by the (o-carboranyl)diphosphine gold(I) complex 1. The resulting α-CF3 substituted carbene complexes 3-R have been characterized by multi-nuclear NMR spectroscopy as well as X-ray crystallography (for 3-Ph). The bonding situation was thoroughly assessed by computational means, showing stabilization of the electrophilic carbene center by π-donation from the aryl substituent and backdonation from Au, as enhanced by the chelating P^P ligand. Reactivity studies under stoichiometric and catalytic conditions substantiate typical carbene-type behavior for 3-Ph.

C-C Cross-Couplings from a Cyclometalated Au(III) C ∧ N Complex: Mechanistic Insights and Synthetic Developments.

In recent years, the reactivity of gold complexes was shown to extend well beyond π-activation and to hold promises to achieve selective cross-couplings in several C-C and C-E (E=heteroatom) bond forming reactions. Here, with the aim of exploiting new organometallic species for cross-coupling reactions, we report on the Au(III)-mediated C(sp2 )-C(sp) occurring upon reaction of the cyclometalated complex [Au(CCH2 N)Cl2 ] (1, CCH2 N=2-benzylpyridine) with AgPhCC. The reaction progress has been monitored by NMR spectroscopy, demonstrating the involvement of a number of key intermediates, whose structures have been unambiguously ascertained through 1D and 2D NMR analyses (1 H, 13 C, 1 H-1 H COSY, 1 H-13 C HSQC and 1 H-13 C HMBC) as well as by HR-ESI-MS and X-ray diffraction studies. Furthermore, crystallographic studies have serendipitously resulted in the authentication of zwitterionic Au(I) complexes as side-products arising from cyclization of the coupling product in the coordination sphere of gold. The experimental work has been paralleled and complemented by DFT calculations of the reaction profiles, providing valuable insight into the structure and energetics of the key intermediates and transition states, as well as on the coordination sphere of gold along the whole process. Of note, the broader scope of the cross-coupling at the Au(III) CCH2 N centre has also been demonstrated studying the reaction of 1 with C(sp2 )-based nucleophiles, namely vinyl and heteroaryl tin and zinc reagents. These reactions stand as rare examples of C(sp2 )-C(sp2 ) cross-couplings at Au(III).

Gold(I)/Gold(III) Catalysis that Merges Oxidative Addition and π-Alkene Activation.

Heteroarylation of alkenes with aryl iodides was efficiently achieved with a (MeDalphos)AuCl complex through AuI /AuIII catalysis. The possibility to combine oxidative addition of aryl iodides and π-activation of alkenes at gold is demonstrated for the first time. The reaction is robust and general (>30 examples including internal alkenes, 5-, 6-, and 7-membered rings). It is regioselective and leads exclusively to trans addition products. The (P,N) gold complex is most efficient with electron-rich aryl substrates, which are troublesome with alternative photoredox/oxidative approaches. In addition, it provides a very unusual switch in regioselectivity from 5-exo to 6-endo cyclization between the Z and E isomers of internal alkenols.

Spin crossover in Fe(triazole)-Pt nanoparticle self-assembly structured at the sub-5 nm scale.

A main goal of molecular electronics is to relate the performance of devices to the structure and electronic state of molecules. Among the variety of possibilities that organic, organometallic and coordination chemistries offer to tune the energy levels of molecular components, spin crossover phenomenon is a perfect candidate for elaboration of molecular switches. The reorganization of the electronic state population of the molecules associated to the spin crossover can indeed lead to a significant change in conductivity. However, molecular spin crossover is very sensitive to the environment and can disappear once the molecules are integrated into devices. Here, we show that the association of ultra-small 1.2 nm platinum nanoparticles with FeII triazole-based spin crossover coordination polymers leads to self-assemblies, extremely well organized at the sub-3 nm scale. The quasi-perfect alignment of nanoparticles observed by transmission electron microscopy, in addition to specific signature in infrared spectroscopy, demonstrates the coordination of the long-chain molecules with the nanoparticles. Spin crossover is confirmed in such assemblies by X-ray absorption spectroscopic measurements and shows unambiguous characteristics both in magnetic and charge transport measurements. Coordinating polymers are therefore ideal candidates for the elaboration of robust, well-organized, hybrid self-assemblies with metallic nanoparticles, while maintaining sensitive functional properties, such as spin crossover.

Bidimensional lamellar assembly by coordination of peptidic homopolymers to platinum nanoparticles.

A key challenge for designing hybrid materials is the development of chemical tools to control the organization of inorganic nanoobjects at low scales, from mesoscopic (~µm) to nanometric (~nm). So far, the most efficient strategy to align assemblies of nanoparticles consists in a bottom-up approach by decorating block copolymer lamellae with nanoobjects. This well accomplished procedure is nonetheless limited by the thermodynamic constraints that govern copolymer assembly, the entropy of mixing as described by the Flory-Huggins solution theory supplemented by the critical influence of the volume fraction of the block components. Here we show that a completely different approach can lead to tunable 2D lamellar organization of nanoparticles with homopolymers only, on condition that few elementary rules are respected: 1) the polymer spontaneously allows a structural preorganization, 2) the polymer owns functional groups that interact with the nanoparticle surface, 3) the nanoparticles show a surface accessible for coordination.

Redox Catalysis Facilitates Lignin Depolymerization.

Lignin is a recalcitrant and underexploited natural feedstock for aromatic commodity chemicals, and its degradation generally requires the use of high temperatures and harsh reaction conditions. Herein we present an ambient temperature one-pot process for the controlled oxidation and depolymerization of this potent resource. Harnessing the potential of electrocatalytic oxidation in conjugation with our photocatalytic cleavage methodology, we have developed an operationally simple procedure for selective fragmentation of ß-O-4 bonds with excellent mass recovery, which provides a unique opportunity to expand the existing lignin usage from energy source to commodity chemicals and synthetic building block source.