Synthesis of Organotantalum Alkyne Complexes [{η5:σ-Me2C(C5H4)(C2B10H10)}TaMe(η2-R1C≡CR2)] and Their Reactions with Unsaturated Molecules

Yang，Jingting1; Xie，Zuowei1,2

2023

10.1021/acs.organomet.3c00061

Organometallics   Impact Factor & Quartile

0276-7333

1520-6041

Hydrogenolysis of tantalum methyl complex [Ta(L)Me] (1, L = [η:σ-MeC(CH)(CBH)]) in the presence of terminal or internal alkynes RC≡CR gave the corresponding π-alkyne complexes [TaL(η-RC≡CR)Me] (2a-2g) in 71-93% yields. Their reactions with various kinds of unsaturated molecules were investigated. Complex 2b reacted with trimethylsilyl acetylene to give an η-butadienyl complex 3. Complexes 2a-2c reacted with XylNC to give aza-η-butadienyl complexes 5a-5c via the η-iminoacyl η-alkyne intermediates 4a-4c. Treatment of 2f with CO in the presence of 1,2-bis(dimethylphosphino)ethane (dmpe) afforded a tantallafuran complex 6. The reaction of 2a with PhNCO produced an oxo N-alkenyl η-iminoacyl complex 7, whereas 2b reacted with PhNCO to generate a metallacyclic complex 8. The structures of these complexes have been confirmed by single-crystal X-ray analyses.

SCI

English

Corresponding

NSFC/RGC Joint Research Scheme[N_CUHK402/18]

Chemistry

Chemistry, Inorganic & Nuclear ; Chemistry, Organic

WOS:000963614500001

AMER CHEMICAL SOC

CHEMISTRY

2-s2.0-85151395804

Scopus

1.Department of Chemistry and State Key Laboratory of Synthetic Chemistry,The Chinese University of Hong Kong,Hong Kong,Shatin, New Territories,Hong Kong
2.Shenzhen Grubbs Institute and Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China

Yang，Jingting,Xie，Zuowei. Synthesis of Organotantalum Alkyne Complexes [{η5:σ-Me2C(C5H4)(C2B10H10)}TaMe(η2-R1C≡CR2)] and Their Reactions with Unsaturated Molecules[J]. Organometallics,2023.

Yang，Jingting,&Xie，Zuowei.(2023).Synthesis of Organotantalum Alkyne Complexes [{η5:σ-Me2C(C5H4)(C2B10H10)}TaMe(η2-R1C≡CR2)] and Their Reactions with Unsaturated Molecules.Organometallics.

Yang，Jingting,et al."Synthesis of Organotantalum Alkyne Complexes [{η5:σ-Me2C(C5H4)(C2B10H10)}TaMe(η2-R1C≡CR2)] and Their Reactions with Unsaturated Molecules".Organometallics (2023).