The dual role of cis-[RuCl₂(dmso)₄] in the synthesis of new water-soluble Ru(II)-phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous-organic biphasic systems

详细信息    查看全文

• 作者：Antal Udvardy ; Attila Csaba B¨¦nyei ; ¨¢gnes Kath¨®
• 关键词：Water-soluble phosphanes ; Ruthenium ; Allylic alcohols ; Isomerization ; Biphasic catalysis
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 出版时间：15 October, 2012
• 年：2012
• 卷：717
• 期：Complete
• 页码：116-122
• 全文大小：573 K

文摘

New air-stable, water-soluble Ru(II)-phosphane complexes were synthesized in high purity by the reaction of cis-[RuCl₂(dmso)₄] with 2 equivalents of 1,3,5-triaza-7-phosphaadamantane (pta) and its N-methyl and N-benzyl derivatives (pta-Me and pta-Bn, respectively). All new complexes were characterized by elementary analysis and spectroscopic methods (NMR, ESI-MS) and the molecular structures of cis-cis-trans-[RuCl₂(dmso)₂(pta)₂], cis-cis-trans-[RuCl₂(dmso)₂(pta-H)₂]Cl₂ (obtained in acidic solutions) and that of cis-cis-trans-[RuCl₂(dmso)₂(pta-Me)₂](CF₃SO₃)₂ were determined by single crystal X-ray diffraction.

Under mild conditions, cis-[RuCl₂(dmso)₄] actively catalyzed the transformation of allylic alcohols into the corresponding ketones with 100 % selectivity while in the same reaction the new Ru(II)-pta complexes showed moderate activity and selectivity.