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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Di- and Triazaphospholes as Ligands for Ruthenium(II) and Iridium(III) Complexes
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Di- and Triazaphospholes as Ligands for Ruthenium(II) and Iridium(III) Complexes

机译:二和三氮杂磷鎓化合物作为钌(II)和铱(III)配合物的配体

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摘要

The reaction of the azaphospholes 5-methyl-2-phenyl-1,2,3-diazaphospole (PDAP) and 2-methyl-2-phenyl-1,2,4,3-triazaphospole (PTAP) with the dimers [LMCl2](2) (LM = eta(6)-C6Me6Ru, eta(5)-C5Me5Ir) of ruthenium(II) and iridium(III) only occurs in presence of nucleophiles such as EtOH or H2O leading to their metal-coordination after cleavage of the dimers. [(eta(6)-C6Me6)RuCl2](2) reacts with PDAP and EtOH in the molar ratio 0.5:1:1 to give the phosphorus-coordinated complex (eta(6)-C6Me6)RuCl2(P-PDAP-EtOH) (1). In the case of [(eta(5)-C5Me5)IrCl2](2), the triazaphosphole PTAP was used in the presence of EtOH or H2O yielding the analogous products (eta(5)-C5Me5)IrCl2(P-PTAP center dot EtOH) (2) or (eta(5)-C5Me5)IrCl2(P-PTAP center dot H2O) (3). In 1-3, the former aromatic azaphosphole (sigma(2), lambda(3)-P) has been converted by 1,2 addition of EtOH or H2O to their P=C or P=N double bond with the nucleophiles EtO- and OH- bonded to phosphorus (sigma(2), lambda(3)-P). Complexes 1-3 with a piano-stool configuration were characterized by elemental analysis, P-31 NMR spectroscopy and single-crystal X-ray diffraction.
机译:氮杂磷鎓5-甲基-2-苯基-1,2,3-重氮磷鎓(PDAP)和2-甲基-2-苯基-1,2,4,3-三氮磷鎓(PTAP)与二聚体[LMCl2]的反应(2)(LM =钌(II)和铱(III)的eta(6)-C6Me6Ru,eta(5)-C5Me5Ir)仅在亲核试剂(例如EtOH或H2O)存在时发生,导致它们在裂解后发生金属配位二聚体。 [(eta(6)-C6Me6)RuCl2](2)与PDAP和EtOH反应,摩尔比为0.5:1:1,得到磷配位络合物(eta(6)-C6Me6)RuCl2(P-PDAP-EtOH )(1)。在[(eta(5)-C5Me5)IrCl2](2)的情况下,三氮唑PTAP在EtOH或H2O存在下使用,产生类似产物(eta(5)-C5Me5)IrCl2(P-PTAP中心点EtOH)(2)或(eta(5)-C5Me5)IrCl2(P-PTAP中心点H2O)(3)。在1-3中,通过与亲核试剂EtO- 1,2加到其P = C或P = N双键中的1,2加EtOH或H2O,已转化了先前的芳族氮杂磷(sigma(2),lambda(3)-P)。和OH-结合到磷上(sigma(2),lambda(3)-P)。通过元素分析,P-31 NMR光谱和单晶X射线衍射对具有钢琴凳结构的配合物1-3进行了表征。

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