Speciation and Mechanistic Studies of Chiral Copper(I) Schiff Base Precursors Mediating Asymmetric Carbenoid Insertion Reactions of Diazoacetates into the Si−H Bond of Silanes

2000 ◽  
Vol 19 (15) ◽  
pp. 2896-2908 ◽  
Author(s):  
Les A. Dakin ◽  
Patricia C. Ong ◽  
James S. Panek ◽  
Richard J. Staples ◽  
Pericles Stavropoulos
Keyword(s):  
Schiff Base ◽  
Mechanistic Studies ◽  
Insertion Reactions

C–H Functionalization Reactions of Phenyl and Vinyl Carbocations Paired with Weakly Coordinating Anions

Synlett ◽  
2020 ◽  
Vol 31 (19) ◽  
pp. 1851-1856
Author(s):  
Hosea M. Nelson ◽  
Stasik Popov ◽  
Brian Shao ◽  
Alex L. Bagdasarian ◽  
Benjamin Wigman
Keyword(s):  
High Energy ◽  
Mechanistic Studies ◽  
Insertion Reactions ◽  
Weakly Coordinating Anions ◽  
Recent Developments ◽  
Weakly Coordinating ◽  
Weakly Coordinating Anion

Carbocations have played a central role in the chemical sciences for over a century. In a synthetic setting, most methods utilize stabilized tricoordinate carbocations, while there are far fewer examples of reactions featuring nonstabilized dicoordinate cations. Here, we provide an overview of recent developments in the generation of high-energy carbocations mediated by weakly coordinating anions and the C–H insertion reactions of such carbocations. Moreover, we discuss mechanistic studies of these catalytic C–H insertion reactions aimed at furthering our understanding of the reactive nature of these rarely invoked cationic intermediates.1 Introduction2 Background: Phenyl Carbocations3 Silylium/Carborane-Catalyzed C–H Insertion Reactions of Phenyl Carbocations4 Silane-Fueled, Weakly Coordinating Anion-Catalyzed, Reductive C–H Insertion Reactions of Vinyl Carbocations5 C–H Insertion Reactivity of Vinyl Carbocations under Basic Conditions6 Conclusion and Outlook

scholarly journals Teaching an old carbocation new tricks: Intermolecular C–H insertion reactions of vinyl cations

Science ◽  
2018 ◽  
Vol 361 (6400) ◽  
pp. 381-387 ◽  
Author(s):  
Stasik Popov ◽  
Brian Shao ◽  
Alex L. Bagdasarian ◽  
Tyler R. Benton ◽  
Luyi Zou ◽  
...  
Keyword(s):  
Theoretical Studies ◽  
Computational Studies ◽  
Mechanistic Studies ◽  
Insertion Reactions ◽  
Bond Forming ◽  
The Past ◽  
Carbon Carbon Bond ◽  
Transition Structures ◽  
The Subject ◽  
Experimental And Theoretical Studies

Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium–weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond–forming reactions, including carbon-hydrogen (C–H) insertion into unactivated sp3 C–H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C–H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.

Mechanistic studies on the cobalt(II) Schiff base catalyzed oxidation of olefins by O2

1987 ◽  
Vol 109 (2) ◽  
pp. 374-379 ◽  
Author(s):  
Dorothy E. Hamilton ◽  
Russell S. Drago ◽  
Alan Zombeck
Keyword(s):  
Schiff Base ◽  
Mechanistic Studies ◽  
Oxidation Of Olefins ◽  
Catalyzed Oxidation

Intramolecular Ligand Hydroxylation:  Mechanistic Studies on the Reaction of a Copper(I) Schiff Base Complex with Dioxygen†

1998 ◽  
Vol 37 (9) ◽  
pp. 2134-2140 ◽  
Author(s):  
Sara Ryan ◽  
Harry Adams ◽  
David E. Fenton ◽  
Michael Becker ◽  
Siegfried Schindler
Keyword(s):  
Schiff Base ◽  
Schiff Base Complex ◽  
Mechanistic Studies ◽  
Base Complex

Spin-crossover in an iron(iii) complex showing a broad thermal hysteresis

2021 ◽  
Author(s):  
Cyril Rajnák ◽  
Romana Mičová ◽  
Ján Moncoľ ◽  
Ľubor Dlháň ◽  
Christoph Krüger ◽  
...  
Keyword(s):  
Schiff Base ◽  
Schiff Base Ligand ◽  
Spin Crossover ◽  
Thermal Hysteresis ◽  
Mononuclear Complex ◽  
Hysteresis Width ◽  
Thermally Induced

A pentadentate Schiff-base ligand 3,5Cl-L2− and NCSe− form a iron(iii) mononuclear complex [Fe(3,5Cl-L)(NCSe)], which shows a thermally induced spin crossover with a broad hysteresis width of 24 K between 123 K (warming) and 99 K (cooling).

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