• New bicyclic (alkyl)(amino)carbene (BICAAC) precursor compounds have been prepared ( 5b–d ). Using BICAAC carbenes, five new Pd-PEPPSI complexes 6a–e ) synthetized. The reported characterized by NMR, HRMS and XRD techniques. palladium 6ae shown high activity in Mizoroki–Heck coupling reaction even at as low 100 ppm loading. A series of alkylamino carbenes (where N -aryl = dipp, mes, 2,6-dimet...

Rapid progress in experimental methodology has made it possible to generate and study highly reactive organometallic fragments in the gas phase. While experimental investigations have focused mainly on the reactivity and thermochemical stability of such species [l-7], parallel developments in ab initio theory have provided descriptions of the molecular and electronic structures of these molecul...

The intermolecular gold(I)-catalyzed reaction between arylalkynes and alkenes leads to cyclobutenes by a [2 + 2] cycloaddition, which takes place stepwise, first by formation of cyclopropyl gold(I) carbenes, followed by a ring expansion. However, 1,3-butadienes are also formed in the case of ortho-substituted arylalkynes by a metathesis-type process. The corresponding reaction of alkenes with a...

Although salts of thiazolium cations are known, many readily prepared iodide salts have eluded spectroscopic and structural characterization; herein, data for a variety of such salts are reported. It has been demonstrated that thiazolium cations can be deprotonated to generate S,N-heterocyclic carbenes and their "electron rich olefin" dimers, but use of the former has been largely overshadowed ...

The reactions of β-lactam carbenes with both 3,6-di(2-pyridyl)tetrazine and 3,6-di(4-pyridyl)tetrazine were studied. It was found that β-lactam carbenes reacted with 3,6-di(2-pyridyl)tetrazine to produce 5-triazolo[1,5-a]pyridylpyrrol-2-ones in good yields, while with 3,6-di(4-pyridyl)tetrazine, they afforded pyrido[c]cyclopenta[b]pyrrol-2-ones in moderate yields. Both reactions were proposed t...

Twisted boron-based biradicals featuring unsaturated C2R2 (R=Et, Me) bridges and stabilization by cyclic (alkyl)(amino)carbenes (CAACs) were recently prepared. These species show remarkable geometrical electronic differences with respect to their unbridged counterparts. Herein, a thorough computational investigation on the origin of distinct electrostructural properties is performed. It shown t...