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

doi:10.1021/om980299i

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

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

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*)₂(η²:η²-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 language	English
Pages (from-to)	4875-4883
Number of pages	9
Journal	Organometallics
Volume	17
Issue number	22
DOIs	https://doi.org/10.1021/om980299i
Publication status	Published - Oct 26 1998
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Kaneko, Y., Suzuki, N., Nishiyama, A., Suzuki, T., & Isobe, K. (1998). 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. Organometallics, 17(22), 4875-4883. https://doi.org/10.1021/om980299i

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. / Kaneko, Yuichi; Suzuki, Nobuyuki; Nishiyama, Aki et al.

In: Organometallics, Vol. 17, No. 22, 26.10.1998, p. 4875-4883.

Research output: Contribution to journal › Article › peer-review

Kaneko, Y, Suzuki, N, Nishiyama, A, Suzuki, T & Isobe, K 1998, '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', Organometallics, vol. 17, no. 22, pp. 4875-4883. https://doi.org/10.1021/om980299i

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title = "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",

abstract = "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*)2(η2:η2-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.",

author = "Yuichi Kaneko and Nobuyuki Suzuki and Aki Nishiyama and Takayoshi Suzuki and Kiyoshi Isobe",

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T1 - 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

AU - Kaneko, Yuichi

AU - Suzuki, Nobuyuki

AU - Nishiyama, Aki

AU - Suzuki, Takayoshi

AU - Isobe, Kiyoshi

PY - 1998/10/26

Y1 - 1998/10/26

N2 - 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*)2(η2:η2-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.

AB - 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*)2(η2:η2-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.

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