Peripherally-metallated porphyrins: synthesis and spectra of meso-η1-palladio- and platinioporphyrins and the crystal structures of cis-{PtBr[10,20-diphenylporphyrinatonickel(II)-5-yl](PPh3)2} and trans-{PtBr[10,20-diphenylporphyrin-5-yl](PPh3)2}·0.25CH2Cl2
作者:Dennis P Arnold、Peter C Healy、Margaret J Hodgson、Michael L Williams
DOI:10.1016/s0022-328x(00)00185-6
日期:2000.8
the PPh3 ligands in 15. The NiDPP ring in 15 suffers ruffling typical of peripherally-crowded Ni(II) porphyrins, the pairs of opposite meso carbons being displaced alternately >±0.4 Å out of the C20N4 mean plane The conformations of the phenyl groups of the PPh3 ligands indicate the presence of non-covalent phenyl–porphyrin π–π interactions. These derivatives are the first isolated examples of peripheral
一系列的内消旋-η 1 -palladio(II) -和platinio(II)卟啉含有任一单齿15个族配位体(PPH 3,ASPH 3)或螯合二膦(DPPE,DPPP,DPPF)已经准备由氧化加成的单-和5,15-二苯基卟啉(H 2 DPP)的二溴衍生物为Pd(0)和Pt(0)的前体。产物的特征在于1 H-和31 P-NMR,可见光吸收和质谱以及反式-[PtBr(H 2 DPP)(PPh 3)2 ](14)的X射线晶体结构。0.25CH 2氯2测定了溶剂化物)和顺式-[PtBr(NiDPP)(PPh 3)2 ](15)。尽管由于15中PPh 3配体的拥挤而存在扭曲,但该结构在Pt原子周围显示出近似方形的平面几何形状。15个位置中的NiDPP环受到周围拥挤的Ni(II)卟啉的典型波动,成对的相对介孔碳在C 20 N 4平均平面之外交替移位>± 0.4ÅPPh 3的苯基构象配体表明存在非共价