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 journalArticle

40 Citations (Scopus)

Abstract

The heterobimetallic trinuclear suffido clusters [(Cp*Ir)23-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)23-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)23-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 languageEnglish
Pages (from-to)69-79
Number of pages11
JournalJournal of Organometallic Chemistry
Volume620
Issue number1-2
DOIs
Publication statusPublished - 2001 Feb 15
Externally publishedYes

Fingerprint

Regioselectivity
Alkynes
X ray crystallography
alkynes
Molecular structure
catalytic activity
Catalyst activity
alcohols
Alcohols
Negative ions
Acetals
Catalysts
X Ray Crystallography
synthesis
Molecular Structure
Anions
crack opening displacement
acetals
metathesis
dienes

Keywords

  • Catalytic addition
  • Cluster
  • Crystal structure
  • Iridium
  • Palladium
  • Platinum

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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 journalArticle

@article{4cdf3605ce3e49f6bf0164593ee952a3,
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",
year = "2001",
month = "2",
day = "15",
doi = "10.1016/S0022-328X(00)00619-7",
language = "English",
volume = "620",
pages = "69--79",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "1-2",

}

TY - JOUR

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

UR - http://www.scopus.com/inward/record.url?scp=0002386653&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0002386653&partnerID=8YFLogxK

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

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

M3 - Article

VL - 620

SP - 69

EP - 79

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -