α-Radical Phosphines: Synthesis, Structure, and Reactivity

A series of phosphines featuring a persistent radical were synthesized in two steps by condensation of dialkyl-/diarylchlorophosphines with stable cyclic (alkyl)(amino)carbenes (cAACs) followed by one-electron reduction of the corresponding cationic intermediates. Structural, spectroscopic, and computational data indicate that the spin density in these phosphines is mainly localized on the original carbene carbon from the cAAC fragment; thus, it remains in the α-position with respect to the central phosphorus atom. The potential of these α-radical phosphines to serve as spin-labeled ligands is demonstrated through the preparation of several AuI derivatives, which were also structurally characterized by single-crystal X-ray diffraction

Synthesis and reactivity of α-cationic phosphines: the effect of imidazolinium and amidinium substituents

Mono- and dicationic phosphines have been synthesized through the reaction of chloroimidazolinium or chloroamidinium salts with secondary or primary phosphines respectively. The resulting ligands, which depict a significantly reduced donor ability compared with their neutral analogues, have been used to design Pt(II) and Au(I) complexes that effectively catalyse the hydroarylation of alkynes

Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

We report copper-catalyzed oxidative dehydrogenative carboxyl­ation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)­Cu­(O₂CPh)] (<b>1-O</b>_<b>2</b><b>CPh</b>), formed from [(BPI)­Cu­(PPh₃)₂], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of <b>1-O</b>_<b>2</b><b>CPh</b> with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a <i>tert</i>-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclo­hexane and <i>d</i>₁₂-cyclo­hexane in separate vessels showed that the turnover-limiting step for the ODC of cyclo­hexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amid­ation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu­(II)–amidate > Cu­(II)–imidate > Cu­(II)–benzoate. Consistent with this trend, Cu­(II)–amidates and Cu­(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclo­hexane led to preliminary investig­ation of copper-catalyzed oxidative dehydrogenative amin­ation of cyclo­hexane to generate a mixture of <i>N</i>-alkyl and <i>N</i>-allylic products