Structural Studies of an Array of Mixed Diamine Phosphine Ruthenium(II) Complexes
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- 作者：Christiane Nachtigal ; Samer Al-Gharabli ; Klaus Eichele ; Ekkehard Lindner ; and Hermann A. Mayer
- 刊名：Organometallics
- 出版年：2002
- 出版时间：January 7, 2002
- 年：2002
- 卷：21
- 期：1
- 页码：105 - 112
- 全文大小：128K
- 年卷期：v.21,no.1(January 7, 2002)
- ISSN：1520-6041
文摘
Treatment of RuCl2(
2-Ph2PCH2CH2OCH3)2 with various chelating diamines permittedthe isolation of the corresponding RuCl2(1-Ph2PCH2CH2OCH3)2(diamine) complexes in highyield (diamine = 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-phenylenediamine, 1,8-diaminonaphthalene, 2,2'-bipyridine, 1,10-phenanthroline). In solution,all complexes prefer the trans-chloro cis-phosphine arrangement, as deduced by NMRspectroscopy. X-ray studies showed that in the solid state all three possible isomers of theoctahedral RuCl2P2(diamine) complexes are present. The reaction of the RuCl2(1-Ph2PCH2CH2OCH3)2(diamine) complexes with 1 equiv of AgSbF6, AgBF4, or TlPF6 leads to theabstraction of one chloride by simultaneously coordinating one ether oxygen to rutheniumand forming monocationic [RuCl(1-Ph2PCH2CH2OCH3)(2-Ph2PCH2CH2OCH3)(diamine)]+compounds. If a large excess of silver or thallium salt is used, the dichloro complexes areconverted to the [Ru(2-Ph2PCH2CH2OCH3)2(diamine)]2+ dications. In the case of 1,2-phenylendiamine as coligand, the corresponding dication is only observed in traces. NMRspectroscopic investigations and X-ray structural analyses confirm the 1 and 2 coordinationof the ether-phosphine ligands in the corresponding mono- and dicationic ruthenium(II)complexes.
2-Ph2PCH2CH2OCH3)2 with various chelating diamines permittedthe isolation of the corresponding RuCl2(1-Ph2PCH2CH2OCH3)2(diamine) complexes in highyield (diamine = 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-phenylenediamine, 1,8-diaminonaphthalene, 2,2'-bipyridine, 1,10-phenanthroline). In solution,all complexes prefer the trans-chloro cis-phosphine arrangement, as deduced by NMRspectroscopy. X-ray studies showed that in the solid state all three possible isomers of theoctahedral RuCl2P2(diamine) complexes are present. The reaction of the RuCl2(1-Ph2PCH2CH2OCH3)2(diamine) complexes with 1 equiv of AgSbF6, AgBF4, or TlPF6 leads to theabstraction of one chloride by simultaneously coordinating one ether oxygen to rutheniumand forming monocationic [RuCl(1-Ph2PCH2CH2OCH3)(2-Ph2PCH2CH2OCH3)(diamine)]+compounds. If a large excess of silver or thallium salt is used, the dichloro complexes areconverted to the [Ru(2-Ph2PCH2CH2OCH3)2(diamine)]2+ dications. In the case of 1,2-phenylendiamine as coligand, the corresponding dication is only observed in traces. NMRspectroscopic investigations and X-ray structural analyses confirm the 1 and 2 coordinationof the ether-phosphine ligands in the corresponding mono- and dicationic ruthenium(II)complexes.