Base metal chemistry and catalysis

Anomalous Hydroboration at a Four-Coordinate Ni(II) Diphenylvinylphosphine Complex: Geometric Impacts on Solution Equilibria

“…NMR spectra are reported as a mixture of isomers. 3 J H,H = 6.7 Hz, CH 3 ), 0.60 (dd, 3 J H,P = 11.3 Hz, 3 J H,H = 7.2 Hz, CH 3 ), 0.53 (dd, 3 J H,P = 13.2 Hz, 3 J H,H = 6.8 Hz, CH 3 ), 0.41 (dd, 3 J H,P = 12.3 Hz, 3 J H,H = 6.0 Hz, CH 3 ). −1 ].…”

“…Alterations to metal complex geometries and spin states can have a profound impact on downstream reactivity. , A reliable understanding of the effects of ligand substitution pattern on corresponding metal complex geometry and electronic properties is of importance to predict later chemical reactivity. In this space, metal-containing complexes featuring first-row elements have been leveraged to explore these phenomena, in part owing to their ability to support unpaired electrons. − Recent work has explored metal-based spin-changes as a consequence of ligand hemilability, solvent coordination, , chirality, and secondary coordination sphere protonation effects. , For example, Holland and co-workers described a Co­(I) β-diketiminate complex with a single carbonyl ligand. In the solid state, this compound is formally four-coordinate, engaging a flanking 2,6-diisopropylphenyl ring via an η 2 -CC interaction, giving an S = 0 system.…”

“…J H,P = 12.3 Hz,3 J H,H = 6.0 Hz, 6H, CH 3 ) 13. C{ 1 H} NMR (126 MHz, C 6 D 6 , mixture): δ C = spectrum is provided in the Supporting Information, but data were not tabulated 31.…”

Ynone Co-Coordination at a Nickel Borane Complex: An Assessment of Secondary Coordination Sphere Effects

“…Secondary coordination sphere-modified diphosphine scaffolds incorporating Lewis acidic moieties are viewed as active participants in metal− ligand cooperative reactivity with Lewis basic substrates − a burgeoning area and an increasingly important design concept for small-molecule activation and catalysis. 24 We have advanced the chemistry of such compounds using base transition metals 25 fer, 26 oxidative addition, 27 cyclometalation, 28 and transmetalation. 29 Of the monoborane ligand scaffolds introduced above, in 2023, we reported [Ni(t t bbpe)(η 2 :η 2 -COD)] (t t bbpe = tri-tertbutylboranyldiphosphinoethane, COD = 1,5-cyclooctadiene) and its behavior with nitriles, resulting in [Ni(t t bbpe)(NCR)] 2 dimers, owing to intermolecular B−N interactions (Scheme 1A, left).…”

“…Secondary coordination sphere-modified diphosphine scaffolds incorporating Lewis acidic moieties are viewed as active participants in metal–ligand cooperative reactivity with Lewis basic substrates – a burgeoning area and an increasingly important design concept for small-molecule activation and catalysis . We have advanced the chemistry of such compounds using base transition metals such as iron, cobalt, and nickel, examining fundamental organometallic reactions such as hydride transfer, oxidative addition, cyclometalation, and transmetalation …”