Synthesis, Structures and Properties of C(sp<sup>2</sup>)‐Centered Homo‐ and Hetero‐Nuclear Gold Complexes

The [1,5]-migration reaction has attractedc onsiderable attention from experimentalists andt heoreticians for decades. Although it has been extensively investigated in various systems, studies on pyrrolium derivatives are underdeveloped. Herein, at heoretical study on the reaction mechanism of [1,5]-migrationi nb oth pyrroliuma nd pyrrole derivatives is presented. The results reveal lower activation barriers in [1,5]-migration of electropositive groups (AuPMe 3 and SnH 3 )i np yrrolium derivatives, although the bond dissociation energies of the AuÀNb ond (98.8 kcal mol À1 )a nd SnÀN bond (81.7 kcal mol À1 )a re larger than that of the NÀFb ond (57.6 kcal mol À1 ). The unexpectedly lower activation barriers (4.5 and 4.9 kcal mol À1 for AuPMe 3 and SnH 3 ,r espectively) for [1,5]-migration of electropositive groups,i nc omparison with the [1,5]-fluorine shift, can be attributed to aromaticity stabilizing the transition states, as revealed by significantly negative nucleus-independent chemical shift (NICS) values. Further studies indicate that charge distribution and frontier molecular orbitals also plays ome roles in [1,5]-migration of pyrrolium derivatives.[a] Q.

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Probing Reaction Mechanism of [1,5]‐Migration in Pyrrolium and Pyrrole Derivatives: Activation of a Stronger Bond in Electropositive Groups Becomes Easier

Xie

Zhao

Chen

et al. 2019

Chemistry An Asian Journal

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

et al. 2020

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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.

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Polynuclear organometallic clusters: synthesis, structure, and reactivity studies

Tang

Zhao

2020

Chem. Commun.

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Synthesis, Structures and Properties of C(sp²)‐Centered Homo‐ and Hetero‐Nuclear Gold Complexes

Cited by 4 publications

References 105 publications

Probing Reaction Mechanism of [1,5]‐Migration in Pyrrolium and Pyrrole Derivatives: Activation of a Stronger Bond in Electropositive Groups Becomes Easier

Probing Reaction Mechanism of [1,5]‐Migration in Pyrrolium and Pyrrole Derivatives: Activation of a Stronger Bond in Electropositive Groups Becomes Easier

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

Polynuclear organometallic clusters: synthesis, structure, and reactivity studies

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Synthesis, Structures and Properties of C(sp2)‐Centered Homo‐ and Hetero‐Nuclear Gold Complexes

Cited by 4 publications

References 105 publications

Probing Reaction Mechanism of [1,5]‐Migration in Pyrrolium and Pyrrole Derivatives: Activation of a Stronger Bond in Electropositive Groups Becomes Easier

Probing Reaction Mechanism of [1,5]‐Migration in Pyrrolium and Pyrrole Derivatives: Activation of a Stronger Bond in Electropositive Groups Becomes Easier

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

Polynuclear organometallic clusters: synthesis, structure, and reactivity studies

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Product

Resources

About

Synthesis, Structures and Properties of C(sp²)‐Centered Homo‐ and Hetero‐Nuclear Gold Complexes