Paek Jong Hyub, Song Kyu Ho, Jung Il, Kang Sang Ook, Ko Jaejung
Department of Chemistry, Korea University, Jochiwon, Chungnam.
Inorg Chem. 2007 Apr 2;46(7):2787-96. doi: 10.1021/ic0620900. Epub 2007 Feb 13.
Preparation of a triisocyanide ligand, 1,3,5-tris[(4-isocyano-3,5-diisoproyl-phenyl)ethynyl]benzene (5), is presented. Ligand 5 is obtained in three steps in 76% overall yield. Reaction of 5 with (eta5-Cp*)Rh(Cabs,s')(Cabs,s'= 1,2-S2C2B10H10-S,S') produced the rhodadithiolene adduct [[(eta5-Cp*)Rh(Cabs,s')(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (6). Ligand 5 reacts with Cr(CO)5(THF) to give the triisocyanide complex [[Cr(CO)5(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (8) and with [AuCl(SMe2)] to give the triisocyanide complex [[AuCl(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (9). As revealed by a single-crystal X-ray diffraction study, the C(9)-N(3)-C(61) angle of 5.9 degrees of trichromium complex 8 occurs in the plane of the bridge and the gold center has a slightly bent linear configuration with a Cl(1)-Au(1)-C(21) angle of 175.4(4) degrees . The rhenation and platination of 5 employing [Re(bpy)(CO)3(AN)]PF6 (AN= acetonitrile) and [(CwedgeNwedgeN)PtCl] ((HCwedgeNwedgeN)= 6-phenyl-2,2'-bipyridine) yielded the luminescent Re(I) and Pt(II) complexes. Full characterization includes structural study of complexes 2, 8, and 9.
介绍了三异腈配体1,3,5-三[(4-异氰基-3,5-二异丙基苯基)乙炔基]苯(5)的制备方法。配体5通过三步反应得到，总产率为76%。5与(η5-Cp*)Rh(Cabs,s')(Cabs,s' = 1,2-S2C2B10H10-S,S')反应生成铑二硫烯加合物[(η5-Cp*)Rh(Cabs,s')(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5。配体5与Cr(CO)5(THF)反应得到三异腈配合物[Cr(CO)5(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5，与[AuCl(SMe2)]反应得到三异腈配合物[AuCl(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5。单晶X射线衍射研究表明，三铬配合物8的C(9)-N(3)-C(61)角为5.9度，出现在桥平面内，金中心具有轻微弯曲的线性构型，Cl(1)-Au(1)-C(21)角为175.4(4)度。使用[Re(bpy)(CO)3(AN)]PF6(AN =乙腈)和(C∧N∧N)PtCl= 6-苯基-2,2'-联吡啶)对5进行铼化和铂化反应，得到了发光的Re(I)和Pt(II)配合物。完整的表征包括对配合物2、8和9的结构研究。
