Rühlig Karoline, Mothes Robert, Aliabadi Azar, Kataev Vladislav, Büchner Bernd, Buschbeck Roy, Rüffer Tobias, Lang Heinrich
Technische Universität Chemnitz, Faculty of Natural Sciences, Institute of Chemistry, Inorganic Chemistry, 09107 Chemnitz, Germany.
Leibniz Institute for Solid State and Materials Research IFW Dresden, Helmholtzstraße 20, 01069 Dresden, Germany.
Dalton Trans. 2016 May 10;45(19):7960-79. doi: 10.1039/c5dt03416g.
Successive treatment of the diethyl ester of 3,4-bis(oxamate)phenylene benzoic acid (3,4-bopbH2Et2OH; ) with [Bu4N]OH and MCl2·nH2O (M = Cu, Ni; n = 2, 6) gave, upon extraction into CH2Cl2, binuclear complexes [Bu4N]4[{M(3,4-bopbO)}2CH2] (, M = Cu, Ni) as novel symmetric methylene diesters. In contrast, subsequent addition of [Bu4N]OH and anhydrous NiCl2 to afforded the very hygroscopic [Bu4N]3[Ni(3,4-bopbO)] () instead. In order to verify reaction conditions to achieve the corresponding carboxamides to - as a crucial step for the synthesis of higher generation dendrimers - was shown to react with RNH2 (R = Me (), Pr ()) to [RNH3][tdqc] (R = Me (), Pr (); tdqc = 1,2,3,4-tetrahydro-2,3-dioxo-6-quinoxaline carboxylate) by rearrangement reactions. Alternatively, if was converted first to 3,4-bopbH2EtF () and treated next with PrNH2, the corresponding carboxamide 3,4-bopbH2Et2NPrH () could be obtained in high yields. The reaction of with [Bu4N]OH and MCl2·nH2O (M = Cu, Ni; n = 2, 6) gave conveniently mononuclear [Bu4N]2[M(3,4-bopbNPrH)] (, M = Cu, Ni). After thus optimizing reaction conditions, for the synthesis of higher-branched bis(oxamato) type complexes the (polyamido)amines (en(II)H2), (den(III)H3), (den(V)H5) and (den(X)H10), possessing two, three, five or ten terminal amino groups, were reacted with appropriate equiv. of to give the corresponding carboxamides en(II)(3,4-bopbH2Et2)2 (), den(III)(3,4-bopbH2Et2)3 (), den(V)(3,4-bopbH2Et2)5 () and den(X)(3,4-bopbH2Et2)10 (). Compounds were converted to the corresponding Cu(II)-containing complexes , which were treated with the corresponding equiv. of [Cu(pmdta)][BF4]2 to afford . Complexes of the series and possess two, three, five or ten end-grafted mononuclear {Cu(3,4-bopb)}(2-) and trinuclear {Cu3(3,4-bopb)(pmdta)2}(2+) complex fragments, respectively. The identities of were established by NMR spectroscopy and ESI-MS measurements. For and , ESI-MS, UV/Vis and ESR studies were applied to confirm the identities of these species. The magnetic properties of the {Cu3(3,4-bopb)(pmdta)2}(2+) end-grafted poly(amidoamine) dendrimers were studied by susceptibility measurements vs. temperature to give J values between -112 () and -118 cm(-1) (), which are typically observed for discrete trinuclear Cu(II)-containing bis(oxamato) type complexes.
将3,4 - 双（草酰胺基）亚苯基苯甲酸二乙酯（3,4 - bopbH2Et2OH）依次与[Bu4N]OH和MCl2·nH2O（M = Cu，Ni；n = 2，6）反应，经二氯甲烷萃取后，得到双核配合物[Bu4N]4[{M(3,4 - bopbO)}2CH2]（，M = Cu，Ni），为新型对称亚甲基二酯。相比之下，随后向中加入[Bu4N]OH和无水NiCl2，得到的是极易吸湿的[Bu4N]3[Ni(3,4 - bopbO)]（）。为了验证反应条件以实现相应的羧酰胺，作为合成更高代树枝状大分子的关键步骤，结果表明与RNH2（R = Me（），Pr（））通过重排反应生成[RNH3][tdqc]（R = Me（），Pr（）；tdqc = 1,2,3,4 - 四氢 - 2,3 - 二氧代 - 6 - 喹喔啉羧酸盐）。或者，如果先将转化为3,4 - bopbH2EtF（），然后用PrNH2处理，可以高产率得到相应的羧酰胺3,4 - bopbH2Et2NPrH（）。与[Bu4N]OH和MCl2·nH2O（M = Cu，Ni；n = 2，6）反应可方便地得到单核[Bu4N]2[M(3,4 - bopbNPrH)]（，M = Cu，Ni）。在优化反应条件后，为了合成更高支化的双（草酰胺基）型配合物，使具有两个、三个、五个或十个末端氨基的（聚酰胺）胺（en(II)H2）、（den(III)H3）、（den(V)H5）和（den(X)H10）与适当当量的反应，得到相应的羧酰胺en(II)(3,4 - bopbH2Et2)2（）、den(III)(3,4 - bopbH
