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Lewis acid adducts (BH sub 3 , Me sup + , and Et sup + ) of the. eta. sup 4 and. eta. sup 2 isomers of Cp sup * Ir(thiophene)

Journal Article · · Organometallics; (USA)
DOI:https://doi.org/10.1021/om00117a048· OSTI ID:6330795

The {eta}{sup 4}-thiophene complex Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T) (2), where 2,5-Me{sub 2} is 2,5-dimethylthiophene, reacts with Me{sub 2}S{center dot}BH{sub 3} to give the BH{sub 3} adduct Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T{center dot}BH{sub 3}) (6), demonstrating the unusually high basicity of the sulfur in 2 as compared with that in Me{sub 2}S. Basic amines remove the BH{sub 3} in 6 to give 2. Surprisingly, the isomer Cp{sup *}Ir({eta}{sup 2}-2,5-Me{sub 2}T) (4) also reacts with Me{sub 2}S{center dot}BH to give 6. The 2-methylthiophene analogues of 2 and 4 react similarly to give Cp{sup *}Ir({eta}{sup 4}-2-MeT{center dot}BH{sub 3}) (5), whose structure was determined by X-ray diffraction. Complex 2 also reacts with R{sub 3}O{sup +} (R = Me, Et) to give the S-alkylated thiophene complexes Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T-R){sup +}.

DOE Contract Number:
W-7405-ENG-82
OSTI ID:
6330795
Journal Information:
Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:3; ISSN 0276-7333; ISSN ORGND
Country of Publication:
United States
Language:
English