Fundamental organometallic chemistry under bimetallic influence: driving ß-hydride elimination and diverting migratory insertion at Cu and Ni.

Bimetallic effects on stoichiometric ß-hydride elimination and migratory insertion reactions were examined. Bimetallic reaction conditions drove ß-hydride elimination at Cu, while bimetallic C-B elimination occurred in the absence of ß-hydrogens. The inherent migratory insertion chemistry of alkynes at Ni was diverted under bimetallic reaction conditions to favor C-H deprotonation.

Improvements to the Practical Usability of the "Crystalline Sponge" Method for Organic Structure Determination.

A microwell droplet approach provided high-quality samples in ≥90% yield of the "crystalline sponge", which was exhibited previously as a revolutionary organic structure determination method. The new protocol, from crystal growth to guest soaking, was conducted in 1-7 days (depending on the guest) and was robust toward user errors, marking improvements over existing protocols. Unit cell determination was used as a practical crystal screening metric. These advances improve the practicality of the crystalline sponge technique for characterizing unknown organic molecules.

Synthesis and characterization of heterobimetallic complexes with direct Cu-M bonds (M = Cr, Mn, Co, Mo, Ru, W) supported by N-heterocyclic carbene ligands: a toolkit for catalytic reaction discovery.

Building upon the precedent of catalytically active (NHC)Cu-FeCp(CO)2 complexes, a series of (NHC)Cu-[M] complexes were synthesized via the addition of Na(+)[M](-) reagents to (NHC)CuCl synthons. The different [M](-) anions used span a range of 7 × 10(7) relative nucleophilicity units, allowing for controlled variation of nucleophile/electrophile pairing in the heterobimetallic species. Direct Cu-M bonds (M = Cr, Mn, Co, Mo, Ru, W) formed readily when the bulky IPr carbene was used as a support. Crystallographic characterization and computational examination of these complexes was conducted. For the smaller IMes carbene, structural isomerism was observed when using the weakest [M](-) nucleophiles, with (IMes)Cu-[M] and {(IMes)2Cu}{Cu[M]2} isomers being observed in equilibrium. Collectively, the series of complexes provides a toolbox for catalytic reaction discovery with precise control of structure-function relationships.

trans-Tetra-carbonyl-bis-(tri-phenyl-phosphane-κP)molybdenum(0).

The well known title compound, trans-[Mo(C18H15P)2(CO)4], has not been studied previously by X-ray crystallography, unlike its cis isomer. The complex possesses crystallographically imposed inversion symmetry, with the Mo atom residing on an inversion centre (1a Wyckoff position). The two tri-phenyl-phosphane groups are arranged in a staggered orientation. Each of the phenyl groups exhibits significantly different Mo-P-C-C torsion angles ranging from 2.6 (2) to 179.4 (1)°, most likely due to steric inter-actions based upon their positions relative to the carbonyl ligands.