Reduction–oxidation properties of organotransition-metal complexes. Part 5. The one-electron oxidation of tricarbonyl(η-cyclopentadienyl)-manganese derivatives and the reactivity of the resulting radical cations
作者:Neil G. Connelly、Maureen D. Kitchen
DOI:10.1039/dt9770000931
日期:——
diamagnetic complexes [MnX(η-C5H5–nMen)(CO)3–xLx]+[X = Cl, Br, or I, x= 1 (5) or 2 (6)], via the attack of halogen radicals on (3) or (4). The relation between the oxidation potential, Ep, and k(CO), the force constant for the carbonyl-stretching vibrations, for (1), (2), and [Mn(η-C5H5–nMen)(CO)3] is discussed with reference to that previously reported for the isoelectronic chromium complexes [Cr(η-C6Me6)(CO)2L]
在CH循环伏安研究2氯2表明[锰(η-C 5 H ^ 5- Ñ我Ñ)(CO)3- X大号X ] [ Ñ = 0,1,或5,X = 1,L =膦或亚磷酸酯(1); Ñ = 0或1,X = 2,L =½dppe(DPPE =苯基2 PCH 2 CH 2 PPH 2),PPH 3,或PMePh 2 ]每经历可逆单电子氧化为[锰(η-C 5 H ^ 5– n Me n)(CO)3– x L x ] + [ x = 1(3)或2(4)]。顺磁性阳离子(3)可以通过(1)的银( I)离子氧化化学生成,并且(4)可以与(2)的银( I)离子或重氮离子氧化分离。在具有[N(C反应6 ħ 4 BR- p) 3 ] [的SbCl 4 ],的SbCl 5,溴2或I 2,(1)和(2)得到的反磁性配合物[MNX(η-C 5 H ^ 5- ñ我ñ)(CO) 3- X大号X] + [X =氯,溴,或I,X = 1(5