作者:Zhiyong Yang、Edwin S. Gould
DOI:10.1039/b416975c
日期:——
Solutions of titanium(II), prepared by dissolving titanium wire in mixtures of hydrofluoric and triflic acids, reduce quinones, nitrosodisulfonate anion, and complexes of cobalt(III). When the oxidant is taken in excess, these reactions yield Ti(IV), whereas with excess reductant, the principal product is Ti(III). These reactions are compared with those by Ti(III). Despite differences in rate laws
通过将钛丝溶解在氢氟酸和三氟甲磺酸混合物中制得的钛(II)溶液可还原醌,亚硝基二磺酸根阴离子和钴(III)的配合物。当氧化剂过量时,这些反应产生Ti(IV),而还原剂过量时,主要产物是Ti(III)。将这些反应与通过Ti(III)进行的反应进行比较。尽管速率法有所不同,但很明显两种还原剂(kTiII / kTiIII)的速率比仍远低于10(4),最小选择性对应于形式势的估计差异,在某些情况下为Ti(II),还原剂越强,反应越慢。对于Ti(III)和Ti(II)而言,在[Co(NH3)5X] 2+系列(其中X = F,Cl,Br和I)中的还原,氟络合物的反应比同系物更快,溴和碘配合物最慢,该顺序类似于Eu2 +还原的顺序,但与Cr(II)和Cu(I)的顺序相反。在最初的80-90%反应期间,与过量Ti(II)发生的[Co(NH3)5Br] 2+反应以非常独立于[氧化剂]的速率进行,这表明引发