Lange Steven J., Nie Hanlin, Stern Charlotte L., Barrett Anthony G. M., Hoffman Brian M.
Departments of Chemistry, Northwestern University, Evanston, Illinois 60208, and Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, U.K.
Inorg Chem. 1998 Dec 14;37(25):6435-6443. doi: 10.1021/ic980791u.
The unsymmetrical porphyrazine (tetraazaporphyrin) bearing a single peripheral bis(dimethylamino) functionality, Mg[pz(NMe(2))(2)(Pr)(6)], was prepared by base-catalyzed cross condensation of dipropyl maleonitrile (in excess) with dimethylamino maleonitrile. The freebase (2H[pz(NMe(2))(2)(Pr)(6)]) and centrally metalated forms (M[pz(NMe(2))(2)(Pr)(6)]; M = Ni(II), Cu(II), Mn(III)) were prepared by treatment of Mg[pz(NMe(2))(2)(Pr)(6)] with trifluoroacetic acid and then the appropriate metal salt. PdCl(2) and PtCl(2) were coordinated to the peripheral bis(dimethylamino) chelates, yielding the bimetallic complexes, M[pz(NMe(2))(2)(Pr)(6)]M'Cl(2) (M = Ni, Cu; M' = Pd, Pt). The heteroleptic [N(2)-Pd-S(2)]-capped porphyrazines were prepared readily by substituting the chloride ions of M[pz(NMe(2))(2)(Pr)(6)]PdCl(2) with the dithiolene chelates, maleonitriledithiolate (mnt(2)(-)), benzenedithiolate (bdt(2)(-)), and 1,3-dithiole-2-one-4,5-dithiolate (dmid(2)(-)). The [N(2)-Pt-S(2)] complexes were prepared by reaction of M[pz(NMe(2))(2)(Pr)(6)]PtCl(2) with the dialkyltin-protected dithiolates dibutyltin(toluene-3,4-dithiolate) and dibutyltin(dmit). The peripheral heteroleptic [N(2)-M'-S(2)] core was found to be electroactive for electron-rich dithiolene ligands (bdt(2)(-), E(1/2)(Pd(III)/Pd(II)) = 0.22 V; tdt(2)(-), E(1/2)(Pt(III)/Pt(II)) = 0.20 V; dmid(2)(-), E(1/2)(Pd(III)/Pd(II)) = 0.19 V; dmit(2)(-), E(1/2)(Pt(III)/Pt(II)) = 0.19 V) but not for the relatively electron-poor dithiolene, maleonitriledithiolate (mnt(2)(-)). The X-ray structure of Ni[pz(NMe(2))(2)(Pr)(6)]Pd(mnt) (13) was determined. Crystal data for C(85)H(109)Cl(3)N(24)Ni(2)Pd(2)S(4): space group P2(1)/n; a = 17.435(4) Å, b = 17.982(2) Å, c = 30.577(2) Å; beta = 104.27(2) degrees; Z = 4.
通过双丙基马来腈（过量）与二甲基氨基马来腈的碱催化交叉缩合反应，制备了带有单个外围双（二甲基氨基）官能团的不对称卟啉嗪（四氮杂卟啉），即Mg[pz(NMe(2))(2)(Pr)(6)]。通过用三氟乙酸处理Mg[pz(NMe(2))(2)(Pr)(6)]，然后加入适当的金属盐，制备了游离碱（2H[pz(NMe(2))(2)(Pr)(6)]）和中心金属化形式（M[pz(NMe(2))(2)(Pr)(6)]；M = Ni(II)、Cu(II)、Mn(III)）。PdCl(2)和PtCl(2)与外围双（二甲基氨基）螯合物配位，生成双金属配合物M[pz(NMe(2))(2)(Pr)(6)]M'Cl(2)（M = Ni、Cu；M' = Pd、Pt）。通过用马来腈二硫醇盐（mnt(2)(-)）、苯二硫醇盐（bdt(2)(-)）和1,3 - 二硫杂环戊烯 - 2 - 酮 - 4,5 - 二硫醇盐（dmid(2)(-)）取代M[pz(NMe(2))(2)(Pr)(6)]PdCl(2)中的氯离子，很容易制备出杂配体[N(2)-Pd-S(2)]封端的卟啉嗪。[N(2)-Pt-S(2)]配合物是通过M[pz(NMe(2))(2)(Pr)(6)]PtCl(2)与二烷基锡保护的二硫醇盐二丁基锡（甲苯 - 3,4 - 二硫醇盐）和二丁基锡（dmit）反应制备的。发现对于富电子的二硫醇烯配体（bdt(2)(-)，E(1/2)(Pd(III)/Pd(II)) = 0.22 V；tdt(2)(-)，E(1/2)(Pt(III)/Pt(II)) = 0.20 V；dmid(2)(-)，E(1/2)(Pd(III)/Pd(II)) = 0.19 V；dmit(2)(-)，E(1/2)(Pt(III)/Pt(II)) = 0.19 V），外围杂配体[N(2)-M'-S(2)]核心具有电活性，但对于相对贫电子的二硫醇烯马来腈二硫醇盐（mnt(2)(-)）则没有电活性。测定了Ni[pz(NMe(2))(2)(Pr)(6)]Pd(mnt)（13）的X射线结构。C(85)H(109)Cl(3)N(24)Ni(2)Pd(2)S(4)的晶体数据：空间群P2(1)/n；a = 17.435(4) Å，b = 17.982(2) Å，c = 30.577(2) Å；β = 104.27(2)°；Z = 4。
