Reactivity of Nickel Complexes Bearing P(C=X)P Ligands (X = O, N) Toward Diazoalkanes: Evidence for Phosphorus Ylide Intermediates.

Nickel carbenes are attracting attention for the development of more sustainable catalysts, among others, for cyclopropanation. Intramolecular trapping of a nickel carbene intermediate with an olefin incorporated in a P(C=C)P Ni pincer complex had previously allowed the isolation of a nickelacyclobutane intermediate and a detailed characterization of its reactivity. Herein, we report the reactivity of related nickel pincer complexes bearing a ketone P(C=O)P or an imine P(C=N)P with diazoalkanes as the carbene precursor. The observed reactivity suggests, in both cases, the reaction of the transient nickel carbene with one of the phosphine arms to form phosphorus ylides that subsequently react with the unsaturated backbone. Density functional theory (DFT) calculations are used to shed light on the mechanisms of these reactions.

Cooperative H2 activation at a nickel(0)-olefin centre.

Catalytic olefin hydrogenation is ubiquitous in organic synthesis. In most proposed homogeneous catalytic cycles, reactive M-H bonds are generated either by oxidative addition of H2 to a metal centre or by deprotonation of a non-classical metal dihydrogen (M-H2) intermediate. Here we provide evidence for an alternative H2-activation mechanism that instead involves direct ligand-to-ligand hydrogen transfer (LLHT) from a metal-bound H2 molecule to a metal-coordinated olefin. An unusual pincer ligand that features two phosphine ligands and a central olefin supports the formation of a non-classical Ni-H2 complex and the Ni(alkyl)(hydrido) product of LLHT, in rapid equilibrium with dissolved H2. The usefulness of this cooperative H2-activation mechanism for catalysis is demonstrated in the semihydrogenation of diphenylacetylene. Experimental and computational mechanistic investigations support the central role of LLHT for H2 activation and catalytic semihydrogenation. The product distribution obtained is largely determined by the competition between (E)-(Z) isomerization and catalyst degradation by self-hydrogenation.

Reactions of Nickel(0)-Olefin Pincer Complexes with Terminal Alkynes: Cooperative C-H Bond Activation and Alkyne Coupling.

Metal-ligand cooperation can facilitate the activation of chemical bonds, opening reaction pathways of interest for catalyst development. In this context, olefins occupying the central position of a diphosphine pincer ligand (PC=CP) are emerging as reversible H atom acceptors, e.g., for H2 activation. Here, we report on the reactivity of nickel complexes of PC=CP ligands with a terminal alkyne, for which two competing pathways are observed. First, cooperative and reversible C-H bond activation generates a Ni(II) alkyl/alkynyl complex as the kinetic product. Second, in the absence of a bulky substituent on the olefin, two alkyne molecules are incorporated in the ligand structure to form a conjugated triene bound to Ni(0). The mechanisms of these processes are studied by density functional theory calculations supported by experimental observations.

Divergent Reactivity of an Isolable Nickelacyclobutane.

Nickelacyclobutanes are mostly invoked as reactive intermediates in the reaction of nickel carbenes and olefins to yield cyclopropanes. Nevertheless, early work suggested that other decomposition routes such as ß-hydride elimination and even metathesis could be accessible. Herein, we report the isolation and characterization of a stable pentacoordinated nickelacyclobutane incorporated in a pincer complex. The coordination of different coligands to the nickelacyclobutane determines its selective decomposition along cyclopropanation, metathesis or apparent ß-hydride elimination pathways. DFT calculations shed light on the mechanism of these different pathways.