Details

Autor(en) / Beteiligte

• Wang, Shichun
• Wang, Dongwei
• Heng, Yi
• Li, Tongyu
• Ding, Wanjian
• Zi, Guofu
• Walter, Marc D.

Titel

Synthesis and Structure of [η5‑1,2,4-(Me3Si)3C5H2]2Th(bipy) and Its Reactivity toward Small Molecules

Ist Teil von

• Inorganic chemistry, 2024-04, Vol.63 (16), p.7473-7492

Ort / Verlag

American Chemical Society

Erscheinungsjahr

2024

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Halide exchange of (Cp3tms)2ThCl2 (1; Cp3tms = η5-1,2,4-(Me3Si)3C5H2) with Me3SiI furnishes (Cp3tms)2ThI2 (2), which is then reduced with potassium graphite (KC8) in the presence of 2,2′-bipyridine to give the thorium bipyridyl metallocene (Cp3tms)2Th­(bipy) (3) in good yield. Complex 3 was fully characterized and readily reacted with various small molecules. For example, 3 may serve as a synthetic equivalent for the (Cp3tms)2Th­(II) fragment when exposed to CuI, Ph2S2, organic azides, and CS2. Moreover, upon the addition of thiobenzophenone Ph2CS, p-methylbenzaldehyde (p-MeC6H4)­CHO, benzophenone Ph2CO, amidate PhCONH­(p-tolyl), seleno-ketone (p,p′-dimethoxy), selenobenzophenone (p-MeOPh)2CSe, di­(p-tolyl)­methanimine (p-tolyl)2CNH, 1,2-di­(benzylidene)­hydrazine (PhCHN)2, and nitriles PhCN, PhCH2CN, and Ph2CHCN C–C coupling results to give (Cp3tms)2Th­[(bipy)­(Ph2CS)] (8), (Cp3tms)2Th­[(bipy)­(p-MePhCHO)] (9), (Cp3tms)2Th­[(bipy)­(Ph2CO)] (10), (Cp3tms)2Th­[(bipy)­{(p-tolylNH)­(Ph)­CO}] (11), (Cp3tms)2Th­[(bipy)­{(p-MeOPh)2CSe}] (12), (Cp3tms)2Th­[(bipy)­{(p-tolyl)2CNH}] (13), (Cp3tms)2Th­[(bipy)­(PhCHNNCHPh)] (14), (Cp3tms)2Th­[(bipy)­(PhCN)] (16), (Cp3tms)2Th­[(bipy)­(PhCH2CN)] (17), and (Cp3tms)2Th­[(bipy)­(Ph2CHCN)] (18), respectively. However, when thiazole is added to 3, the dimeric sulfido complex [(Cp3tms)2Th]2[μ-(bipy)­CH2NCHCHS]2 (15) can be isolated. Moreover, the addition of isonitriles such as Me3CNC and PhCH2NC to 3 results in C–N bond cleavage and C–C coupling processes to form the thorium isocyanido amido complexes (Cp3tms)2Th­[4-(Me3C)­bipy]­(NC) (19) and (Cp3tms)2Th­[4-(PhCH2)­bipy]­(NC) (20), respectively. Nevertheless, upon exposure of 3 to (trimethylsilyl)­diazomethane Me3SiCHN2, the bis-amido complex (Cp3tms)2Th­[5,6-(Me3SiCH)­bipy] (21), concomitant with N2 release, is isolated.