Metal–ligand cooperation by aromatization–dearomatization as a tool in single bond activation

Milstein, David

doi:10.1098/rsta.2014.0189

Cited by 106 publications

(63 citation statements)

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“…95 This water splitting reactivity was described in more detail in recent reviews 87. 96 Activation of water by an NCN pincer complex containing a central NHC ligand and two pyridine arms was also reported by Morris et al. Dearomatization of one or both Py arms by a CH 2 Py group deprotonation was observed in these systems 97…”

Section: Metal–ligand Cooperation Through Aromatization/dearomatizsupporting

confidence: 57%

Metal–Ligand Cooperation

2015

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Metal-ligand cooperation (MLC) has become an important concept in catalysis by transition metal complexes both in synthetic and biological systems. MLC implies that both the metal and the ligand are directly involved in bond activation processes, by contrast to "classical" transition metal catalysis where the ligand (e.g. phosphine) acts as a spectator, while all key transformations occur at the metal center. In this Review, we will discuss examples of MLC in which 1) both the metal and the ligand are chemically modified during bond activation and 2) bond activation results in immediate changes in the 1st coordination sphere involving the cooperating ligand, even if the reactive center at the ligand is not directly bound to the metal (e.g. via tautomerization). The role of MLC in enabling effective catalysis as well as in catalyst deactivation reactions will be discussed.

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Section: Metal–ligand Cooperation Through Aromatization/dearomatizsupporting

confidence: 57%

Metal–Ligand Cooperation

2015

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“…The cooperation between the metal center and the so-called noninnocent ligands enables novel catalytic reactivity facilitated by concerted substrate activation and dual-site-driven catalytic transformations. 294−297…”

Section: Mechanistic Complexity In Catalysis By 3d Transition Metalsmentioning

confidence: 99%

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

et al. 2018

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Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies to enable the rational in silico catalyst design. The versatile reactivity and nontrivial electronic structure effects, common for systems based on 3d transition metals, introduce additional complexity that may represent a particular challenge to the standard computational strategies. In this review, we discuss the challenges and capabilities of modern electronic structure methods for studying the reaction mechanisms promoted by 3d transition metal molecular catalysts. Particular focus will be placed on the ways of addressing the multiconfigurational problem in electronic structure calculations and the role of expert bias in the practical utilization of the available methods. The development of density functionals designed to address transition metals is also discussed. Special emphasis is placed on the methods that account for solvation effects and the multicomponent nature of practical catalytic systems. This is followed by an overview of recent computational studies addressing the mechanistic complexity of catalytic processes by molecular catalysts based on 3d metals. Cases that involve noninnocent ligands, multicomponent reaction systems, metal–ligand and metal–metal cooperativity, as well as modeling complex catalytic systems such as metal–organic frameworks are presented. Conventionally, computational studies on catalytic mechanisms are heavily dependent on the chemical intuition and expert input of the researcher. Recent developments in advanced automated methods for reaction path analysis hold promise for eliminating such human-bias from computational catalysis studies. A brief overview of these approaches is presented in the final section of the review. The paper is closed with general concluding remarks.

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“…2 Among others, lutidine-derived metal complexes, which are readily deprotonated at the pincer methylene arms with concomitant dearomatization of the pyridine central moiety, have received significant attention. 3 Both lutidine-and NH-containing pincer complexes have provided highly active and selective catalysts for a broad variety of hydrogenation 4 and dehydrogenation reactions. 5 Recently, the Milstein group has reported novel Ru complexes incorporating lutidine-based PNN(H) ligands containing secondary amines as side donors that are efficient catalysts in the (de)hydrogenation of polar substrates.…”

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confidence: 99%