Abstract
The hydrogensulfido-bridged diiridium complex [ClCp*Ir(μ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(μ3-S)2 core [(Cp*Ir)2(μ3-S)2RuCl 2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(μ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(μ3-S)2RuMe(dppe)][PF 6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl 2)Ir}(μ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(μ3-S)2(μ-H) 2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(μ3-S)2RuCl(CO)(PPh 3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(μ3-S)2RuCl(CNXy)(PPh 3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(μ3-S)2Ru(CNXy) 2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(μ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(μ3-S)2RuCl(depe)][BPh 4] 4′, 5′CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.
| Original language | English |
|---|---|
| Pages (from-to) | 2575-2582 |
| Number of pages | 8 |
| Journal | Journal of the Chemical Society - Dalton Transactions |
| Issue number | 15 |
| Publication status | Published - 1999 Aug 7 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex. / Kochi, Takuya; Nomura, Yasuo; Tang, Zhen; Ishii, Youichi; Mizobe, Yasushi; Hidai, Masanobu.
In: Journal of the Chemical Society - Dalton Transactions, No. 15, 07.08.1999, p. 2575-2582.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex
AU - Kochi, Takuya
AU - Nomura, Yasuo
AU - Tang, Zhen
AU - Ishii, Youichi
AU - Mizobe, Yasushi
AU - Hidai, Masanobu
PY - 1999/8/7
Y1 - 1999/8/7
N2 - The hydrogensulfido-bridged diiridium complex [ClCp*Ir(μ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(μ3-S)2 core [(Cp*Ir)2(μ3-S)2RuCl 2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(μ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(μ3-S)2RuMe(dppe)][PF 6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl 2)Ir}(μ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(μ3-S)2(μ-H) 2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(μ3-S)2RuCl(CO)(PPh 3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(μ3-S)2RuCl(CNXy)(PPh 3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(μ3-S)2Ru(CNXy) 2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(μ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(μ3-S)2RuCl(depe)][BPh 4] 4′, 5′CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.
AB - The hydrogensulfido-bridged diiridium complex [ClCp*Ir(μ-SH)2IrCp*Cl] reacted with [RuH2(PPh3)4] to give a mixed-metal trinuclear cluster with an Ir2Ru(μ3-S)2 core [(Cp*Ir)2(μ3-S)2RuCl 2(PPh3)] 2, which was further converted into the cationic diphosphine derivatives [(Cp*Ir)2(μ3-S)2RuCl(L)]Cl (L = dppe = Ph2PCH2CH2PPh2 3 or depe = Et2PCH2CH2PEt2 4). The reaction of cluster 3 with Me2CuLi followed by anion metathesis with KPF6 afforded the cationic methyl cluster [(Cp*Ir)2(μ3-S)2RuMe(dppe)][PF 6] 5 in good yield, while treatment of 3 with CHCl2Li led to selective formation of [(Cp*Ir){(η4-C5Me5CHCl 2)Ir}(μ3-S)2RuCl(dppe)] 6, in which one of the Cp* ligands was alkylated by CHCl2Li to form an η4-diene. Clusters 3 and 4 were also transformed into the dihydrido clusters [(Cp*Ir)2(μ3-S)2(μ-H) 2Ru(L)] (L = dppe 7 or depe 8) by the reaction with NaBH4. On the other hand, cluster 2 was converted into the carbonyl cluster [(Cp*Ir)2(μ3-S)2RuCl(CO)(PPh 3)]Cl 9, the isocyanide clusters [(Cp*Ir)2(μ3-S)2RuCl(CNXy)(PPh 3)]Cl 10 (Xy = 2,6-C6H3Me2) and [(Cp*Ir)2(μ3-S)2Ru(CNXy) 2(PPh3)][BPh4]2 11 and the co-ordinatively unsaturated thiolato clusters [(Cp*Ir)2(μ3-S)2Ru(SAr)2] (Ar = 2,4,6-C6H2Pri3 12 or Xy 13) on treatment with CO, XyNC and LiSAr, respectively. The molecular structures of [(Cp*Ir)2(μ3-S)2RuCl(depe)][BPh 4] 4′, 5′CH2Cl2, 6, 7 and 12·2C6H6 were established by X-ray diffraction studies.
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UR - http://www.scopus.com/inward/citedby.url?scp=33748607213&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:33748607213
SP - 2575
EP - 2582
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1472-7773
IS - 15
ER -