Nicholson T L, Mahmood A, Refosco F, Tisato F, Müller P, Jones A G
The Department of Radiology, Harvard Medical School, Boston, Massachusetts 02215.
Inorganica Chim Acta. 2009 Aug 1;362(10):3637-3640. doi: 10.1016/j.ica.2009.04.017.
The nitrosyl complex H[TcNOCl(4)] reacts with the tridentate ligand bis[(2-diphenylphosphino)propyl]amine (PNPpr) to yield a mixture of the mer or fac isomers of [TcCl(2)(NO)(PNPpr)]. In acetonitrile, where the ligand is freely soluble, reaction occurs at room temperature to yield mostly the mer isomer with the linear nitrosyl ligand cis to the amine ligand; and the phosphine ligands arranged in a mutually trans orientation. The reaction in methanol requires reflux to dissolve the lipophilic ligand and generates the fac isomer of [TcCl2(NO)(PNPpr)] as the major product, with the tridentate ligand in a facial arrangement, leaving the chlorides and nitrosyl ligand in the remaining facial sites. The steric bulk of the tridentate ligand's diphenylphophino- moieties results in a significant distortion from octahedral geometry, with the P-Tc-P bond angle expanded to 99.48(4)°. The infrared spectra display absorptions from these nitrosyl ligands in the 1700 and 1800 cm(-1) regions for the fac and mer isomers respectively. The ESI(+) mass spectra each display the parent ion at 647 m/z.
亚硝酰配合物H[TcNOCl(4)]与三齿配体双[(2-二苯基膦基)丙基]胺(PNPpr)反应，生成[TcCl(2)(NO)(PNPpr)]的面式或经式异构体混合物。在乙腈中，配体可自由溶解，室温下反应主要生成经式异构体，其中亚硝酰线性配体与胺配体顺式排列，膦配体相互反式排列。在甲醇中的反应需要回流以溶解亲脂性配体，并生成[TcCl2(NO)(PNPpr)]的面式异构体作为主要产物，三齿配体呈面式排列，氯和亚硝酰配体占据其余的面式位点。三齿配体的二苯基膦基部分的空间位阻导致其显著偏离八面体几何构型，P-Tc-P键角扩大到99.48(4)°。红外光谱显示，面式和经式异构体的这些亚硝酰配体的吸收峰分别在1700和1800 cm(-1)区域。电喷雾电离(+)质谱均显示母离子在647 m/z处。
