Long Yiu Tsang, Wei Bai, Lam Cheung Kong, Herman H. Y. Sung, Ian D. Williams* and Guochen Jia*,
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引用次数: 0
Abstract
While alkyne metathesis reactions involving d0 carbynes (alkylidynes) are well documented, those involving well-defined non-d0 carbynes are still rare. This work reports the synthesis and alkyne metathesis activity of d2 Re(V) carbyne complexes supported by a [LXL]-type monoanionic [PNP]-pincer ligand, a [LLX]-type monoanionic [PNO]-pincer ligand, and a [ONOH]-bidentate ligand derived from the Schiff base 2-[(2-hydroxyphenyl)iminomethyl]phenol. Treatment of Re(≡CCH2Ph)Cl2(PMePh2)3 (1) with bis(2-diphenylphosphino-4-tolyl)amine (PNHP) and 2-{(2-diphenylphosphino-phenyl)iminomethyl}phenol (PNOH) in the presence of NEt3 produced the pincer complexes Re(≡CCH2Ph)Cl(PMePh2)(PNP) (2) and Re(≡CCH2Ph)Cl(PMePh2)(PNO) (3), respectively. The Schiff base 2-[(2-hydroxyphenyl)iminomethyl]phenol (HONOH) reacted with Re(≡CCH2Ph)Cl2(PMePh2)3 (1) to give Schiff base complex Re(≡CCH2Ph)Cl(PMePh2)(ONOH) (4) (ONOH = o-O-C6H4–CH═N-(o-C6H4OH)) bearing a [ONOH]-bidentate ligand. The [PNP]- and [PNO]-pincer complexes are catalytically active for homometathesis of neat 1-methoxy-4-(1-propyn-1-yl)benzene at 150 °C, while the complex bearing the [ONOH]-bidentate Schiff base ligand is catalytically inactive under similar conditions. The energy profiles for metathesis reactions of model pincer rhenium alkyne-carbyne complexes have been calculated with DFT methods.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.