Ligand reactivity in diarylamido/bis(phosphine) PNP complexes of Mn(CO)3 and Re(CO)3.
Ligand reactivity in diarylamido/bis(phosphine) PNP complexes of Mn(CO)3 and Re(CO)3.
复制标题
Mn(CO)3 和 Re(CO)3 的二芳基酰胺/双（膦）PNP 配合物中的配体反应性。
作者：
A. Radosevich;Jonathan G. Melnick;S. Stoian;Deborha Bacciu;Chun;B. Foxman;O. Ozerov;D. Nocera
本文报道了三羰基配位配合物（PNP）Mn（CO）（3）和（PNP）Re（CO）（3）的合成（PNP = [2-P（CHMe（2））（2）-4-MeC（6）H（3）]（2）N（-））。循环伏安图显示两种母体化合物的可逆单电子氧化还原对（对于（PNP）Mn（CO）（3），-0.34 V vs Cp（2）Fe（0/+）;对于（PNP）Re（CO）（3），-0.25 V vs Cp（2）Fe（0/+）），并且用AgOTf的化学氧化导致形成相应的顺磁性三氟甲磺酸盐[（PNP）Mn（CO）（3）]OTf和[（PNP）Re（CO）（3）]OTf。电子顺磁共振谱和计算结果表明，这一事件主要是配体为中心的，烯丙基化的有机配体部分[（PNP）Mn（CO）（3）]OTf与烯丙基三丁基锡烷是符合这一分配。（PNP）Mn（CO）（3）氧化成[（PNP）Mn（CO）（3）]OTf导致平均CO伸缩频率偏移30 cm（-1）;（PNP）Mn（CO）（3）与TfOH质子化形成[（PNHP）Mn（CO）（3）]OTf导致类似的幅度偏移。
The syntheses of meridionally ligated tricarbonyl complexes (PNP)Mn(CO)(3) and (PNP)Re(CO)(3) are described (PNP = [2-P(CHMe(2))(2)-4-MeC(6)H(3)](2)N(-)). Cyclic voltammograms show reversible one-electron redox couples for both parent compounds (-0.34 V vs Cp(2)Fe(0/+) for (PNP)Mn(CO)(3), -0.25 V vs Cp(2)Fe(0/+) for (PNP)Re(CO)(3)), and chemical oxidation with AgOTf results in formation of the corresponding paramagnetic triflate salts [(PNP)Mn(CO)(3)]OTf and [(PNP)Re(CO)(3)]OTf. Electron paramagnetic resonance spectra and computational results indicate that this event is primarily ligand centered; allylation of the organic ligand moiety of [(PNP)Mn(CO)(3)]OTf with allyltributylstannane is consistent with this assignment. The oxidation (PNP)Mn(CO)(3) to [(PNP)Mn(CO)(3)]OTf results in a shift in average CO stretching frequency of 30 cm(-1); protonation of (PNP)Mn(CO)(3) with TfOH to form [(PNHP)Mn(CO)(3)]OTf results in a similar magnitude shift.