Showing papers by "Guochen Jia published in 2004"
TL;DR: The reactivities and the X-ray diffraction data of osmabenzynes indicate that these metallacycles have aromatic properties.
Abstract: The synthesis and chemical and structural properties of metallabenzynes are reviewed. Reaction of [OsCl2(PPh3)3] with HC⋮CSiMe3 produces the osmabenzyne [Os(⋮CC(SiMe3)C(CH3)C(SiMe3)CH)Cl2(PPh3)2], which undergoes electrophilic substitution reactions with HBF4 and Br2 to give new osmabenzynes. The reactivities and the X-ray diffraction data of osmabenzynes indicate that these metallacycles have aromatic properties. Unlike benzyne, which is thermally unstable, osmabenzynes are thermally much more stable and can be stored for months at room temperature without decomposition. The higher thermal stability of osmabenzynes compared to benzyne can be related to the relatively smaller ring strain and larger conjugation energy.
127 citations
TL;DR: Treatment of OsX2(PPh3)3 (X = Cl, Br) with HC⋮CCH(OH)C ⋮CH in THF produces Osmabenzenes as mentioned in this paper.
Abstract: Treatment of OsX2(PPh3)3 (X = Cl, Br) with HC⋮CCH(OH)C⋮CH in THF produces OsX2(CHC(PPh3)CH(OH)C⋮CH)(PPh3)2, which reacts with PPh3 to give osmabenzenes [Os(CHC(PPh3)CHC(PPh3)CH)X2(PPh3)2]+.
111 citations
TL;DR: In this paper, the metal−η3-allyl interaction in an endo isomer of Ru(d)-to-CO(π*) back-bonding interaction was investigated.
57 citations
TL;DR: In this article, the carbyne complexes [OsCl3(CCH2R)(PPh3)2] with NEt3 were obtained from the reactions of the reaction of the carborene complexes with HCCR.
Abstract: Treatment of [OsCl2(PPh3)3] with HCCR (R = Ph, p-tolyl, CMe3) in the presence of HCl gives the corresponding trichloro(carbyne) complexes [OsCl3(CCH2R)(PPh3)2] in good yields. The vinylidene complexes [OsCl2(=C=CHR)(PPh3)2] (R = Ph, p-tolyl, CMe3) are, in turn, prepared from the reactions of the carbyne complexes [OsCl3(CCH2R)(PPh3)2] with NEt3. These new vinylidene complexes are hygroscopic
24 citations
TL;DR: In this article, the synthesis and chemical and structural properties of metallabenzynes are reviewed and the reactivities and X-ray diffraction data of osmabenzys indicate that these metallacycles have aromatic properties.
Abstract: The synthesis and chemical and structural properties of metallabenzynes are reviewed. Reaction of [OsCl2(PPh3)3] with HC⋮CSiMe3 produces the osmabenzyne [Os(⋮CC(SiMe3)C(CH3)C(SiMe3)CH)Cl2(PPh3)2], which undergoes electrophilic substitution reactions with HBF4 and Br2 to give new osmabenzynes. The reactivities and the X-ray diffraction data of osmabenzynes indicate that these metallacycles have aromatic properties. Unlike benzyne, which is thermally unstable, osmabenzynes are thermally much more stable and can be stored for months at room temperature without decomposition. The higher thermal stability of osmabenzynes compared to benzyne can be related to the relatively smaller ring strain and larger conjugation energy.