Molybdenum-Mediated Coupling of Carbon Monoxide to a C3 Product on a Single Metal Site.

The synthesis and characterization of a series of naphthalenediyl-diphosphine molybdenum complexes are reported. A novel dicarbonyl-Mo complex (3) converts to a bis(siloxy)acetylene complex (5) upon reduction and treatment with a silyl electrophile, Me3SiCl. This process shows exclusive C-C coupling distinct from the previously reported phenylene-linked analogue that undergoes C-O cleavage. Further CO catenation can be engendered from 5 under mild conditions providing metallacyclobutenone complex 6, with a C3O3 organic motif derived from CO. Differences in reactivity are assigned to the nature of the arene linker, where the naphthalenediyl fragment shows a propensity for η4 binding previously not observed for phenylene. Consistent with this hypothesis, a Mo precursor with a 1,3-cyclohexadienediyl-based linker was prepared which also showed exclusive formation of a bis(siloxy)acetylene complex and subsequent coupling of a third CO molecule.

Oxidative Coupling with Zr(IV) Supported by a Noninnocent Anthracene-Based Ligand: Application to the Catalytic Cotrimerization of Alkynes and Nitriles to Pyrimidines.

We report the synthesis and reactivity of Zr complexes supported by a 9,10-anthracenediyl-linked bisphenoxide ligand, L. ZrIVLBn2 (1) undergoes facile photolytic reduction with concomitant formation of bibenzyl and ZrIVL(THF)3 (2), which displays a two-electron reduced anthracene moiety. Leveraging ligand-stored reducing equivalents, 2 promotes the oxidative coupling of internal and terminal alkynes to isolable zirconacyclopentadiene complexes, demonstrating the reversible utilization of anthracene as a redox reservoir. With diphenylacetylene under CO, cyclopentadienone is formed stoichiometrically. 2 is competent for the catalytic formation of pyrimidines from alkynes and nitriles. Mechanistic studies suggest that selectivity for pyrimidine originates from preferred formation of an azazirconacyclopentadiene intermediate, which reacts preferentially with nitriles over alkynes.

A Convenient Synthetic Protocol to 1,2-Bis(dialkylphosphino)ethanes.

1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step.