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 › peer-review

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

Access to Document

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

Cite this

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 › peer-review

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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",

note = "Funding Information: This work was supported by a Grant-in-aid for Specially Promoted Research (09102004) from the Ministry of Education, Science, Sports, and Culture, Japan. ",

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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

N1 - Funding Information: This work was supported by a Grant-in-aid for Specially Promoted Research (09102004) from the Ministry of Education, Science, Sports, and Culture, Japan.

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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