Synthesis and structures of heterobimetallic Ir2M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes

Dai Masui; Takuya Kochi; Zhen Tang; Youichi Ishii; Yasushi Mizobe; Masanobu Hidai

doi:10.1016/S0022-328X(00)00619-7

Synthesis and structures of heterobimetallic Ir₂M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes

Dai Masui, Takuya Kochi, Zhen Tang, Youichi Ishii, Yasushi Mizobe, Masanobu Hidai

Research output: Contribution to journal › Article

41 Citations (Scopus)

Abstract

The heterobimetallic trinuclear suffido clusters [(Cp*Ir)₂(μ₃-S)₂MCl₂] (M = Pd (3), Pt (4); Cp* = η⁵-C₅Me₅) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH)₂IrCp*Cl] (2) and [MCl₂(COD)] (COD = cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh₃)₄] afforded the cationic trinuclear cluster [(Cp*Ir)₂(μ₃-S)₂PdCl(PPh ₃)]Cl (5). Clusters 3 and 4 reacted with PPh₃ to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir)₂(μ₃-S)₂M(dppe)][BPh ₄]₂ (M = Pd (9), Pt (10); dppe = Ph₂PCH₂CH₂PPh₂) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH₂Cl₂, 9·CH₃COCH₃, and 10·CH₃COCH₃ were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst.

Original language	English
Pages (from-to)	69-79
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	620
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(00)00619-7
Publication status	Published - 2001 Feb 15
Externally published	Yes

Keywords

Catalytic addition
Cluster
Crystal structure
Iridium
Palladium
Platinum

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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Masui, D., Kochi, T., Tang, Z., Ishii, Y., Mizobe, Y., & Hidai, M. (2001). Synthesis and structures of heterobimetallic Ir₂M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes. Journal of Organometallic Chemistry, 620(1-2), 69-79. https://doi.org/10.1016/S0022-328X(00)00619-7

Synthesis and structures of heterobimetallic Ir₂M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes. / Masui, Dai; Kochi, Takuya; Tang, Zhen; Ishii, Youichi; Mizobe, Yasushi; Hidai, Masanobu.

In: Journal of Organometallic Chemistry, Vol. 620, No. 1-2, 15.02.2001, p. 69-79.

Research output: Contribution to journal › Article

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title = "Synthesis and structures of heterobimetallic Ir2M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes",

abstract = "The heterobimetallic trinuclear suffido clusters [(Cp*Ir)2(μ3-S)2MCl2] (M = Pd (3), Pt (4); Cp* = η5-C5Me5) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH)2IrCp*Cl] (2) and [MCl2(COD)] (COD = cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh3)4] afforded the cationic trinuclear cluster [(Cp*Ir)2(μ3-S)2PdCl(PPh 3)]Cl (5). Clusters 3 and 4 reacted with PPh3 to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir)2(μ3-S)2M(dppe)][BPh 4]2 (M = Pd (9), Pt (10); dppe = Ph2PCH2CH2PPh2) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH2Cl2, 9·CH3COCH3, and 10·CH3COCH3 were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst.",

keywords = "Catalytic addition, Cluster, Crystal structure, Iridium, Palladium, Platinum",

author = "Dai Masui and Takuya Kochi and Zhen Tang and Youichi Ishii and Yasushi Mizobe and Masanobu Hidai",

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T1 - Synthesis and structures of heterobimetallic Ir2M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes

AU - Masui, Dai

AU - Kochi, Takuya

AU - Tang, Zhen

AU - Ishii, Youichi

AU - Mizobe, Yasushi

AU - Hidai, Masanobu

PY - 2001/2/15

Y1 - 2001/2/15

N2 - The heterobimetallic trinuclear suffido clusters [(Cp*Ir)2(μ3-S)2MCl2] (M = Pd (3), Pt (4); Cp* = η5-C5Me5) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH)2IrCp*Cl] (2) and [MCl2(COD)] (COD = cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh3)4] afforded the cationic trinuclear cluster [(Cp*Ir)2(μ3-S)2PdCl(PPh 3)]Cl (5). Clusters 3 and 4 reacted with PPh3 to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir)2(μ3-S)2M(dppe)][BPh 4]2 (M = Pd (9), Pt (10); dppe = Ph2PCH2CH2PPh2) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH2Cl2, 9·CH3COCH3, and 10·CH3COCH3 were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst.

AB - The heterobimetallic trinuclear suffido clusters [(Cp*Ir)2(μ3-S)2MCl2] (M = Pd (3), Pt (4); Cp* = η5-C5Me5) were synthesized from the dinuclear hydrogensulfido complex [Cp*IrCl(μ-SH)2IrCp*Cl] (2) and [MCl2(COD)] (COD = cycloocta-1,5-diene), while the reaction of 2 with [Pd(PPh3)4] afforded the cationic trinuclear cluster [(Cp*Ir)2(μ3-S)2PdCl(PPh 3)]Cl (5). Clusters 3 and 4 reacted with PPh3 to give a series of mono and dicationic clusters including 5, while the dicationic clusters [(Cp*Ir)2(μ3-S)2M(dppe)][BPh 4]2 (M = Pd (9), Pt (10); dppe = Ph2PCH2CH2PPh2) were obtained by the reaction with dppe followed by anion metathesis. The molecular structures of 5·CH2Cl2, 9·CH3COCH3, and 10·CH3COCH3 were determined by X-ray crystallography. Clusters 3 and 4 were found to catalyze the addition of alcohols to alkynes to give the corresponding acetals. Internal 1-aryl-1-alkynes were transformed by cluster 3 into the corresponding 2,2-dialkoxy-1-arylalkanes with high regioselectivity up to 99:1, while cluster 4 was a much less regioselective catalyst.

KW - Catalytic addition

KW - Cluster

KW - Crystal structure

KW - Iridium

KW - Palladium

KW - Platinum

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U2 - 10.1016/S0022-328X(00)00619-7

DO - 10.1016/S0022-328X(00)00619-7

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VL - 620

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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