Dinuclear oxidative addition reactions using an isostructural series of Ni₂, Co₂, and Fe₂ complexes

Abstract

A family of low-valent Ni, Co, and Fe naphthyridine-diimine (NDI) complexes is presented. Ligand-based π* orbitals are sufficiently low-lying to fall within the metal 3d manifold, resulting in electronic structures that are highly delocalized across the conjugated [NDI]M system. This feature confers stability to metal-metal interactions during two-electron redox reactions, as demonstrated in a prototypical oxidative addition of allyl chloride.

Selective Synthesis of a Series of Isostructural MIICuI Heterobimetallic Complexes Spontaneously Assembled by an Unsymmetrical Naphthyridine‐Based Ligand

“…The rigid naphthyridine core promotes a close interaction between two transition metals, and additional donor groups may be incorporated to enforce open binding sites for exploration of metal‐metal cooperativity in reaction chemistry . Moreover, naphthyridine‐based bimetallic complexes have been shown to catalyze a range of reactions . However, these mostly symmetrical systems have so far been used to study homobimetallic complexes.…”

“…[21] Rigid, naphthyridine-based ligands are suitable candidates for addressing these issues. [26][27][28][29][30][31] However, these mostly symmetrical systems have so far been used to study homobimetallic complexes. [23][24][25] Moreover,n aphthyridine-based bimetallicc omplexes have been shown to catalyzearange of reactions.…”

“…[23][24][25] Moreover,n aphthyridine-based bimetallicc omplexes have been shown to catalyzearange of reactions. [26][27][28][29][30][31] However, these mostly symmetrical systems have so far been used to study homobimetallic complexes. Indeed, upon treatment with mixtures of differentm etals, symmetrical ligandsa re expected to yield am ixture of products rather than one well-defined heterobimetallic complex.…”

“…Notably,X -ray crystallography is limited in its ability to do so because it does not provide information on the bulk sample, and elements with similar electron densities (e.g. Zn II and Cu I )a re often difficult to distinguish crystallographically.T herefore, av ariety of techniquesw ere employed to determinet he selectivity of the synthetic routes to heterobimetallic complexes 1-M.F irst, these syntheses yield as ingle product, as determined by 1 Ha nd 31 PNMR spectroscopy,f or diamagnetic 1-Zn ( Figure S29). However,N MR spectroscopy is of less value for other 1-M complexesd ue to their paramagnetism.…”

Butadienyl Diiron Complexes: Nonplanar Metalla‐Aromatics Involving σ‐Type Orbital Overlap

“…Thus, we can reason that the Fe-Fe interaction functions as a "super atom" which closes the cycle as found for related dimeric complexes in the literature, such as a dicobalt unit with an alkyne bridging ligand compared to the butadienyl ligand here, [20] and a dinickel unit also involving d-d orbital interactions in a large metallacycle. [21,22] The nucleus-independent chemical shift (NICS) [23] is often used to computationally gauge the aromaticity. Here we used Multiwfn program [24] to find a representative plane of the nonplanar ferracycles Fe1-C1-C2-C3-C4 or Fe2-C1-C2-C3-C4 via the least square method, and computed NICS(1) zz values at the geometrical center of the ferracycles and the normal vector of the plane.…”