Reactions of di-tert-butyldiphosphatetrahedrane (tBuCP)2 with various carbenes result in P–P or P–C bond cleavage to afford phosphaalkenes and phosphirenes. The results demonstrate the distinct reactivity compared its monomer tBuCP.

In the presence of carbon monoxide, ruthenium carbenes give a net insertion/ring expansion (Buchner reaction) into one of the aromatic rings of the N-heterocyclic carbene ligand. In alkene metathesis applications, the N-heterocyclic carbene ligand is both robust and typically inert to reactions with the metal-bound carbene. This unique reaction is completely regioselective. The complexes obtain...

N-heterocyclic carbenes (NHCs), typically derived from imidazolium salts, have provided highly powerful ligands for catalysis. Recently, abnormal C4 bonding rather than normal C2 bonding has been discovered as a new carbene bonding mode. We were interested in comparing the consequences of these two bonding modes on the metal center. Therefore we synthesized related palladium complexes 1 and 2 c...

the effects of halogens; fluorine, chlorine and bromine, on the stability and multiplicity of phenylcarbenes / silylenes/ germylenes structures are compared and contrasted at b3lyp/6-311++g**//b3lyp/6-31+g* level. the singlet-triplet energy gaps, δes-t , values for all the above speciesincrease through fluorinated up, δes-ts and δehomo–lumos support the stability of the singlet statesinspite of...

Alkylidene carbenes undergo rapid inter- and intramolecular reactions rearrangements, including 1,2-migrations of β-substituents to generate alkynes. Their propensity for substituent migration exerts profound influence over the broader utility alkylidene carbene intermediates, yet prior efforts categorize 1,2-migratory aptitude in these elusive species have been hampered by disparate modes gene...