Kappa what? Insights into the coordination modes of NP ligands.

While first synthesized more than three decades ago, complexes supported by NP ligands have seen renewed interest due to the synthesis of new ligands, expansion of their reactivity, and catalytic applications. Possessing both soft phosphines and hard nitrogen donors, NP ligands can accommodate various metal geometries and coordination modes thanks to their capability to act as bidentate, tridentate or tetradentate ligands. This short review will explore how metals bind to these ligands and also highlight the complexes' reactivity and catalytic abilities.

Mechanistic Studies of ε-Caprolactone Polymerization by (salen)AlOR Complexes and a Predictive Model for Cyclic Ester Polymerizations.

Aluminum alkoxide complexes () of salen ligands with a three-carbon linker and para substituents having variable electron-withdrawing capabilities (X = NO, Br, OMe) were prepared, and the kinetics of their ring-opening polymerization (ROP) of ε-caprolactone (CL) were investigated as a function of temperature, with the aim of drawing comparisons to similar systems with two-carbon linkers investigated previously (). While and exhibit saturation kinetics and similar dependences of their ROP rates on substituents X (invariant , similar Hammett ρ = +1.4(1) and 1.

One-electron Ni(II)/(I) redox couple: potential role in hydrogen activation and production.

The three-coordinate Ni(I) complex Ni(Cl)(P(2)), where P(2) is the diphosphine (iPr)DPDBFphos, reacts with the acids HCl·(dioxane) and 2,6-lutidinium chloride to generate Ni(H)(Cl)(P(2)) and Ni(Cl)(2)(P(2)). Photolysis of the Ni(H)(X)(P(2)) (for X = Cl, Br) results in formation of H(2) and the Ni(I) halide. This reaction also proceeds in reverse when heated.

Synthesis and reactivity of an isolable cobalt(I) complex containing a β-diketiminate-based acyclic tetradentate ligand.

A model for cobalamin was synthesized using a new monoanionic tetradentate nitrogen donor ligand; 2-(4-tolyl)-1,3-bis(2-isopropylpyridyl)propenediimine (Tol-BDI((2-pp)2)H) (1), which utilizes isopropylpyridines as pendant arms on a β-diketiminate (BDI) backbone. During the synthesis of 1, the rearrangement product, Tol-BDI((2-pp)(4-pp))H (2) was observed. Metalation of 1 with zinc iodide and cobalt chloride yielded the corresponding Tol-BDI((2-pp)2)ZnI (3) and Tol-BDI((2-pp)2)CoCl (4) complexes.

First-row transition-metal chloride complexes of the wide bite-angle diphosphine (iPr)DPDBFphos and reactivity studies of monovalent nickel.

The diphosphine 4,6-bis(3-diisopropylphosphinophenyl)dibenzofuran (abbreviated as (iPr)DPDBFphos) has been metalated with transition metal dichlorides of zinc, cobalt, and nickel to yield ((iPr)DPDBFphos)MCl(2) complexes. Within these compounds, the diphosphine (iPr)DPDBFphos adapts a wide range of bite angles (115 to 180°) as determined by X-ray crystallography. A three-coordinate planar Ni(I) species was isolated from the reduction of ((iPr)DPDBFphos)NiCl(2) with KC(8).