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 | |
| Publication status | Published - 2001 Feb 15 |
| Externally published | Yes |
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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 journal › Article
}
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
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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 -