کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1310146 | 975233 | 2008 | 9 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Chalcogenolato-bridged cyclometallated binuclear palladium complexes: Synthesis, spectroscopy, structures of [Pd2(μ-Cl)(μ-SMes)(C10H6NMe2–C,N)2] and [Pd2(μ-SePh)2(C10H6NMe2–C,N)2] Chalcogenolato-bridged cyclometallated binuclear palladium complexes: Synthesis, spectroscopy, structures of [Pd2(μ-Cl)(μ-SMes)(C10H6NMe2–C,N)2] and [Pd2(μ-SePh)2(C10H6NMe2–C,N)2]](/preview/png/1310146.png)
Reactions of orthometallated binuclear palladium complexes with NaER, obtained by NaBH4 reduction of R2E2 in methanol, gave complexes, [Pd2(μ-ER)2(C∩Y)2] (HC∩Y = N,N-dimethylbenzylamine (C6H5CH2NMe2), N,N-dimethylnaphthylamine (C10H7NMe2), tri-o-tolylphosphine {P(tol-o)3}; ER=SePh, SeMes, TePh, TeMes (Mes = 2,4,6-Me3C6H2). Similar reactions of [Pd2(μ-Cl)2(C10H6NMe2–C,N)2] with Pb(SMes)2 or MesSH in the presence of NaHCO3 gave chloro/thiolato-bridged complex [Pd2(μ-Cl)(μ-SMes)(C10H6NMe2–C,N)2]. The newly synthesized complexes were characterized by elemental analysis, UV–Vis, IR, NMR (1H, 13C, 31P, 77Se, 125Te) spectroscopy. These complexes crystallized out preferentially in sym-cis configuration. A low energy charge transfer transition has been identified from chalcogenolate centers to an emptyπ∗ orbital of cyclometallated ligand in absorption spectroscopy in these complexes. The structures of [Pd2(μ-Cl)(μ-SMes)(C10H6NMe2–C,N)2] (1) and [Pd2(μ-SePh)2(C10H6NMe2–C,N) 2] (3) have been established by single crystal X-ray diffraction analyses. In the former, the two palladium atoms are held together by chloro and thiolato bridges whereas in the latter, the two phenylselenolato ligands bridge two palladium atoms. The pyrolysis of [Pd(μ-TeMes)(C10H6NMe2–C,N)]2 (10) in a furnace gave Pd7Te3 whereas thermolysis in TOPO afforded primarily PdTe2.
Chalcogenolato-bridged cyclometallated binuclear palladium complexes of the type [Pd2(μ-ER)2(C∩Y)2] (HC∩Y = N,N-dimethylbenzylamine (C6H5CH2NMe2), N,N-dimethylnaphthylamine (C10H7NMe2), tri-o-tolylphosphine {P(tol-o)3}; ER = SePh, SeMes, TePh, TeMes) and [Pd2(μ-Cl)(μ-SMes)(C10H6NMe2–C,N)2] have been prepared and characterized by elemental analysis, UV–Vis and NMR spectroscopy. A LLCT band has been identified from chalcogenolate centers to an empty π∗ orbital of the cyclometallated ligand. In the molecular structure of [Pd2(μ-SePh)2(C10H6NMe2–C,N)2] two phenylselenolate ligands bridge two palladium atoms. The pyrolysis of [Pd(μ-TeMes)(C10H6NMe2–C,N)]2 in a furnace yields Pd7Te3.Figure optionsDownload as PowerPoint slide
Journal: Inorganica Chimica Acta - Volume 361, Issue 8, 2 June 2008, Pages 2462–2470