Reactions of terminal and bridging thiol di-μ-methylene dirhodium complexes with alkynes to afford the corresponding ethenethiolate complexes. Remarkable C-C bond formation between two μ-CH2 and alkynes on the bridging ethenethiolate complexes

Yuichi Kaneko, Nobuyuki Suzuki, Aki Nishiyama, Takayoshi Suzuki, Kiyoshi Isobe

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14 Citations (Scopus)


The reaction of the terminal dithiol complex trans-[(RhCp*)2(μ-CH2)2(SH) 2] (1, Cp* = η5-C5Me5) with dialkyl acetylenedicarboxylate gives the terminal bis(ethenethiolate) complex trans-[(RhCp*)2(μ-CH2)2(SCR 1=CHR2)2] (2a, R1, R2 = COOMe; 2b, R1, R2 = COOEt). Treatment of the cationic bridging thiol complex [(RhCp*)2(μ-CH2)2(μ-SH)](BPh 4) (3) with dimethyl acetylenedicarboxylate or carbyl propiolate very easily gives the bridging ethenethiolate complex [(RhCp*)2(μ-CH2)2(μ-SCR 1=CHR2)](BPh4) (4a, R1, R2 = COOMe; 4b, R1 = H, R2 = COOPh; 4c, R1 = H, R2 = COOMe). Although complex 2 is not able to react further with alkyne, complex 4 does and forms the butadiene complex [(RhCp*)222-μ-CH 2=CR3-CR4=CH2)(μ-SCR 1=CHR2)](BPh4) (5a, R1, R2, R3, R4 = COOMe; 5a-Et2, R1, R2 = COOMe, R3, R4 = COOEt; 5a-Et1, R1, R2 = COOMe, R3 = H, R4 = COOEt; 5b, R1 = H, R2 = COOPh, R3, R4 = COOMe; 5c, R1 = H, R2 = COOMe, R3, R4 = COOMe). The structures of complexes 2b, 4a, and 5a have been confirmed by an X-ray diffraction study.

Original languageEnglish
Pages (from-to)4875-4883
Number of pages9
Issue number22
Publication statusPublished - Oct 26 1998
Externally publishedYes


ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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