N Functionalization via Molybdenum-Nitride Complex: Stepwise BH Bond Additions.

Reactivity of (triphosphine)Mo-nitrido complex generated by N splitting, toward boranes is reported. The simple adduct Mo≡N→BH is observed with BH.SMe while 1,2 addition is evidenced with 9-BBN leading to H-Mo=NBR.

One Ligand to Bind them All: S~C~S Carbon- and Sulfur-Based Gem-Dianion as Structuring Ligand for Iron Polymetallic Assemblies.

Numerous synthetic models of the FeMo-co cluster of nitrogenases have been proposed to find the simplest structure with relevant reactivity. Indeed, such structures are able to perform multi-electrons reduction processes, such as the conversion of N to ammonia, and of CO into methane and alkenes. The most challenging parameter to imitate is indeed the central carbide ligand, which is believed to maintain the integrity of iron sulfide assembly during the course of catalytic cycles.

Ammonia Synthesis at Room Temperature and Atmospheric Pressure from N : A Boron-Radical Approach.

Ammonia, NH , is an essential molecule, being part of fertilizers. It is currently synthesized via the Haber-Bosch process, from the very stable dinitrogen molecule, N and dihydrogen, H . This process requires high temperatures and pressures, thereby generating ca 1.

Catalytic Reduction of N to Borylamine at a Molybdenum Complex.

Catalytic formation of borylamines from atmospheric N is achieved for the first time using a series of homogenous (triphosphine)Mo complexes. Stepwise functionalization of the (triphosphine)Mo-nitrido complex with chloroborane led to the synthesis of the imido complex. Electrochemical characterization of the (PPP)Mo-nitrido and (PPP)Mo-borylimido complexes showed that the latter is much more easily reduced.

Double α,α CH bond insertion into sp CH moiety: synthesis of a Fe carbene bis-hydride dinitrogen complex.

Reduction of high spin paramagnetic complex [(κ2-P, P'-PCH2PCy)FeCl2] 2 by two electrons under N2 resulted in the formation of two isomeric low spin diamagnetic complexes 3trans and 3cis [Fe(κ3-P,C,P'-PCPCy)(H)2(N2)]. Cristallization allowed isolation of complex 3d [Fe(κ3-P,C,P'-PCPCy)(H)2]2(μ-N2), characterized by X-ray diffraction, Mössbauer and Raman spectroscopies. DFT calculations rationalized the facile double α,α CH bond insertion into a single sp3 CH2 moiety, as well as the fast exchange positions of the hydrides in the cis dihydride complex observed by NMR spectrocscopy.

Geminal Dianions Stabilized by Main Group Elements.

This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e., geminal dianions, stabilized by main group elements.

Triphos-Fe dinitrogen and dinitrogen-hydride complexes: relevance to catalytic N reductions.

The two electron reduction of iron complexes [(PP)Fe(Cl)] (R = Ph or tBu) 2a-b afforded complexes [(PP)Fe(N)] 4a-b. Protonation of 4a at the metal center and subsequent reduction to Fe(i)-H species lead to complex [(PP)Fe(N)(H)] 6avia a spontaneous disproportionation reaction. Complex 4a behaves as one of the most efficient monometallic Fe-catalysts reported to date for N-to-N(SiMe) functionalization under atmospheric pressure.

Room-Temperature Functionalization of N to Borylamine at a Molybdenum Complex.

Intermolecular, stepwise functionalization by BH bonds of a (triphosphine)Mo -nitrido complex generated by N splitting is reported. The imido-hydride and di-hydride-amido Mo complexes have been isolated and characterized. Addition of PinBH to the [Mo(H) (N(BPin) )] complex at room temperature results in the liberation of borylamines from the metal center.

Synthesis and Reactivity of an End-Deck cyclo-P Iron Complex.

Reduction of the Fe complex [( PP )FeCl ] (2) generated an electron-rich and unsaturated Fe species, which was reacted with white phosphorus. The resulting new complex, [( PP )Fe(η -P )] (3), is the first iron cyclo-P complex and the only known stable end-deck cyclo-P complex outside Group V. Complex 3 features an Fe center, as shown by Mössbauer spectroscopy, associated to a P fragment.

C-H Bond Trifluoromethylation of Arenes Enabled by a Robust, High-Valent Nickel(IV) Complex.

The robust, high-valent Ni complex [(Py) Ni F (CF ) ] (Py=pyridine) was synthesized and fully characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. It reacts with aromatic compounds at 25 °C to form the corresponding benzotrifluorides in nearly quantitative yield. The monomeric and dimeric Ni CF complexes 2⋅Py and 2 were identified as key intermediates, and their structures were unambiguously determined by EPR spectroscopy and X-ray diffraction.

A Nucleophilic Gold(III) Carbene Complex.

The first Au carbene complex was prepared by reacting a geminal dianion with a (P,C) cyclometalated Au precursor. Its structure and bonding situation have been thoroughly investigated by experimental and computational means. The presence of a high-energy highest occupied molecular orbital (HOMO) centered at the carbene center suggests nucleophilic character for the Au carbene complex.

Transmetalation of a nucleophilic carbene fragment: from early to late transition metals.

Early transition metal nucleophilic carbene complexes have been used as stoichiometric carbene transfer agents in a transmetalation process.