Bi- and tetrametallic complexes of the noble metals with PNP-ligands

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• 作者：Christian Sarcher ; Sergei Lebedkin ; Manfred M. Kappes ; Olaf Fuhr ; Peter W. Roesky
• 关键词：Chelates ; Gold ; Luminescence ; Multimetallic compounds ; Palladium ; Photoluminescence ; Platinum ; P-N-P ligands
• 刊名：Journal of Organometallic Chemistry
• 出版年：1 February, 2014
• 年：2014
• 卷：751
• 期：Complete
• 页码：343-350
• 全文大小：1264 K

文摘

Two new ligands with {(Ph₂P)₂N} functions have been synthesized and introduced into the chemistry of gold(I). The first ligand N,N-bis(diphenylphosphanyl)-4-(phenyldiazenyl)aniline (DPPPA) is a derivative of an azo dye. Reaction of DPPPA with [(tht)AuCl] (tht聽=聽tetrahydrothiophene) in CH₂Cl₂ gave the dye functionalized bimetallic gold(I) complex [DPPPA(AuCl)₂] (1). The second ligand, m-N,N,N鈥?em>,N鈥?tetrakis(diphenylphosphanyl)xylylenediamine, (DPPXA), has two {(Ph₂P)₂N} functional groups in a xylylenediamine backbone. DPPXA was reacted with [(tht)AuCl] to give the tetrametallic gold complex [DPPXA(AuCl)₄] (2). Reaction of DPPXA with [(COD)MCl₂] (M聽=聽Pd, Pt) (COD聽=聽1,5-cyclooctadiene) in DMSO resulted in the bimetallic palladium and platinum complexes [DPPXA(MCl₂)₂] (M聽=聽Pd (3), Pt (4)). DPPPA and all metal complexes were characterized by single crystal X-ray diffraction. The complexes demonstrate quite different photophysical properties. Whereas no photoluminescence (PL) was detected for 1 and 4, complex 2 shows red PL in methylene chloride solution as well as in the solid state. Near-infrared emission at 鈭?00聽nm was observed for complex 3 at temperatures below 鈭?0聽K.