Isolation of cationic and neutral (allenylidene)(carbene) and bis(allenylidene)gold complexes.

Isolation of cationic and neutral (allenylidene)(carbene) and bis(allenylidene)gold complexes† †Electronic supplementary information (ESI) available. CCDC 1418631–1418633. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03654b Click here for additional data file. Click here for additional data file.

A new method for the preparation of N-stabilized allenylidene complexes of chromium and tungsten

Displacement of tetrahydrofuran in [(CO)5M(THF)] (M /Cr, W) by the anion [C /C /C( /X)Y] (X /O; NR; Y /NR ? 2, Ph) followed by alkylation of the resulting metalate with [R ƒ 3 O]BF4 (R ƒ /Me, Et) offers a convenient and versatile route to p-donorsubstituted allenylidene complexes, [(CO)5M /C /C /C(XR ƒ)Y]. Allenylidene complexes in which the terminal carbon atom of the allenylidene ligand const...

Pyrrolyl substituted allenylidene complexes of ruthenium.

Pyrrolyl and indolyl substituted allenylidene complexes of ruthenium have been prepared from the trapping of cationic trans-[Cl(dppm)(2)Ru=C=C=C=CH(2)](+) with various pyrroles or N-methylindole. The reaction is rationalized as involving regioselective attack of the organometallic electrophile on the electron-rich heterocycle followed by proton migration to the terminal =CH(2) entity of the int...

Synthesis of electronically modified Ru-based neutral 16 VE allenylidene olefin metathesis precatalysts.

Electronic modifications within Ru-based olefin metathesis precatalysts have provided a number of new complexes with significant differences in reactivity profiles. So far, this aspect has not been studied for neutral 16 VE allenylidenes. The first synthesis of electronically altered complexes of this type is reported. Following the classical dehydration approach (vide infra) modified propargyl...

Bis(allenylidene) Complexes of Palladium and Platinum

trans-Bis(alkynyl)palladium complexes, trans-[(PEt3)2Pd(-CtCC{dO}NR2)2] (NR2 = NMe2 (2a), N(CH2)4 (2b)), were synthesized by two different methods: (a) by copper-catalyzed reaction of HCtCC(dO)NR2with [PdCl2(PEt3)2] under basic conditions and (b) by treatingHCtCC(dO)NR2 with AgNO3 followed by transmetalation of the alkynyl ligand from silver to [PdCl2(PEt3)2]. The reaction of AgCtCC(dO)NMe2 (3a...