Metal‐Metal Cooperation in Dinucleating Complexes Involving Late Transition Metals Directed towards Organic Catalysis

Abstract

Cooperatively bimetallic organic catalysis, coupling actions of two metal centers in a catalytic organic transformation via co‐activation of a single molecule or synergistic activation of two molecules, has witnessed rapid development in the last decades. This cooperative reacting mode creates new catalytic platforms to facilitate the characterization of bimetallic reaction pathways, offers remarkable improvements to some well‐established reactions, or exhibit unprecedented reactivity. Herein, we demonstrate perspectives of some significant contributions in the field of cooperatively bimetallic organic catalysis using dinucleating complexes with late transition metals. Based on different activation modes for the catalysis, the major advances are classified into: (1) bimetallic co‐activation of small molecules; (2) bimetallic co‐activation of single molecules; (3) bimetallic dual‐activation of two molecules. The mechanisms are also discussed to facilitate the understanding of the way of the metal‐metal cooperation involved in the catalytic cycles.

Selective cleavage of unactivated arene ring C–C bonds by iridium: key roles of benzylic C–H activation and metal–metal cooperativity

“…Metal-metal cooperativity is increasingly recognized as a key factor in enabling difficult organic transformations at discrete metal complexes. 55,56 Although the role of metal-metal cooperativity in arene C-C bond activation has received little attention, previously reported C-C oxidative additions in benzene, 16 biphenylene, 15 cyclopentadienyl 18 and cyclooctatetraene ligands 28,29 suggested the involvement of reactive intermediates with the anti arrangement of the two metal centers. The difference in reactivities of anti and syn isomers of these intermediates, however, have not been studied, and the role of the anti geometry in enabling cooperativity in C-C bond scission remains to be enumerated.…”

Advances in Single‐Atom Nanozymes Research†

“…Single‐atom nanozymes (SAzymes) possess uniformly dispersed metal species with well‐defined structure and coordination environment, which are conductive to identification of active sites, and facilitate studies of catalytic mechanism at atomic level. [ 20‐23 ] Furthermore, single‐atom site nanozymes can achieve maximum atom‐utilization efficiency and fully exposed active sites, which has proven to enable to enhance intrinsic catalytic activity of nanozymes. [ 24 ] SAzymes thus have shown a promise to serve as direct surrogates of traditional enzymes by mimicking the highly evolved catalytic center of natural enzymes.…”

DFT Study on Dinuclear Palladium Complex Catalyzed Pyrrole Formation From tert‐Butyl Isocyanide and Alkynes

“…[19] Similar to dinuclear palladium complexes, other dinuclear transition metal complexes have efficient performance on reactivity and selectivity as well due to the bimetallic cooperativity. [20][21][22][23][24][25][26][27][28][29][30][31][32] With the successful preparation of a novel binucleating ligand N, N'-bis[(2-diphenylphosphino) phenyl]formamidine (Hdpfam), [33] Naofumi Tsukada et al have subsequently made significant contributions for the synthesis of homo-and heterobimetallic complexes. [34][35][36][37][38] For example, a dinuclear palladium complex [Pd 2 (t-BuNC) 2 (μ-dpfam)]PF 6 with two isocyanide ligands was synthesized and served as catalyst for pyrrole formation from tert-butyl isocyanide and various alkynes.…”

“…They elucidated the mechanistic pathways of [Pd(μ‐Br) t Bu 3 P] 2 in the equilibrium isomerization part of isomerizing olefin metathesis processes and ultimately use the results to improve the efficiency of these orthogonal tandem processes [19] . Similar to dinuclear palladium complexes, other dinuclear transition metal complexes have efficient performance on reactivity and selectivity as well due to the bimetallic cooperativity [20–32] …”