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Dinuclear molybdenum(II) carboxylates systems with nitrogen donor ligands of biological importance.

机译：具有核生物供体配体的双核钼（II）羧酸盐系统。

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摘要

This study focuses on the coordination chemistry observed in the reactions of dinuclear molybdenum(II) carboxylate compounds with nitrogen donor ligands and discusses the potential biological application of the resulting complexes. All compounds were synthesized from (MO{dollar}rmsb2(Osb2CR)sb2(MeCN)sb6rbracklbrack BFsb4rbracksb2{dollar} (R = CH{dollar}sb3{dollar} and CHF{dollar}sb2){dollar} starting materials. Products include a "trimer-of-dimers", {dollar}rm Mosb6(Osb2CCHFsb2)sb{lcub}12{rcub}(bpy)sb4{dollar} (bpy = 2,2{dollar}spprime{dollar}-bipyridine), in which three dinuclear units are joined via axial difluoroacetate bridges. In addition, a novel "dimer-of-dimers" compound, {dollar}rmlbrack Mosb4(Osb2CCHFsb2)sb4{dollar}(1,2-bis(5{dollar} spprime{dollar}-methyl-2,2{dollar}spprime{dollar}-bipyridin-5-yl)ethane){dollar} sb2rbracklbrack BFsb4rbracksb4,{dollar} in which two dinuclear units are bridged via equatorially bound tetradentate chelating ligands has been structurally characterized. The related dinuclear and polymeric products, {dollar}rmlbrack Mosb2(Osb2CCHFsb2)sb2(bpy)sb2(MeCN)(BFsb4)rbracklbrack BFsb4rbrack{dollar} and {dollar}rmlbrack Mosb4(Osb2CCHFsb2)sb8(bpy)sb2rbracksb{lcub}n{rcub},{dollar} have also been isolated and characterized.; A synthetic and electrochemical study of a series of compounds with the general formula {dollar}rmlbrack Mosb2(Osb2CR)sb2{dollar}(N-N){dollar}sb2rbracklbrack {lcub}rm BF{rcub}sb4rbracksb2{dollar} (N-N = bpy, 4,4{dollar}spprime{dollar}-Me{dollar}sb2{dollar}bpy, 5,5{dollar}spprime{dollar}-Me{dollar}sb2{dollar}bpy, and 1,10-phenanthroline; R = CH{dollar}sb3,{dollar} CHF{dollar}sb2,{dollar} and Ph) was initiated to probe the reactivity of the dinuclear system. Extended Huckel Theory calculations were performed to determine the nature of the orbitals populated upon reduction of the dinuclear system. The rich reduction chemistry of these compounds is unusual in that four reduction waves were observed. The first two reversible reductions were determined to be primarily ligand-based processes but with {dollar}sim{dollar}30% metal contribution.; Compounds with the tridentate ligands 1,4,7-triazacyclononane (TACN) and tris-pyrazolylborate (HB(pz){dollar}sb3sp-){dollar} were prepared and crystallographically characterized. {dollar}rmlbrack Mosb2(OAc)sb2(TACN)(MeCN)sb2rbracklbrack BFsb4rbracksb2, lbrack Mosb2(OAc)sb2(TACN)(bpy)rbracklbrack BFsb4rbracksb2, and lbrack Mosb2(OAC)sb2(HB(pz)sb3)(bpy)rbracklbrack BFsb4rbrack{dollar} represent unusual examples of quadruply bonded compounds with only one facially coordinated ligand. These complexes are interesting coordination compounds that also serve as models for the interaction of dinuclear metal centers with nitrogen-donating amino acid side chains.; Unusual coordination modes have been observed for the purine nucleobase derivatives, 9-ethylguanine, 9-ethyladenine, and 1,9-diethyladenine, in which the ligands bridge the dinuclear molybdenum centers via the X6,N7 positions (X = O, N). The resultant compounds, {dollar}rmlbrack Mosb2(Osb2CCHFsb2)sb2{dollar}(9-EtGH){dollar}rmsb2(MeCN)sb2rbrack lbrack BFsb4rbracksb2, lbrack Mosb2(Osb2CCHFsb2)sb2{dollar}(9-{dollar}rm EtAH)sb2(MeCN)sb2rbracklbrack BFsb4rbracksb2,{dollar} and {dollar}rmlbrack Mosb2(OAc)sb2{dollar}(1,9-{dollar}rm Etsb2A)sb2rbracklbrack Irbracksb2{dollar} have been characterized by variable temperature {dollar}sp1{dollar}H NMR, IR, and UV-vis spectroscopies as well as by X-ray diffraction and elemental analysis. These complexes provide models for the potential in vivo interactions of dinuclear carboxylate compounds with DNA.
机译：这项研究的重点是在双核羧酸钼（II）化合物与氮供体配体反应中观察到的配位化学，并讨论了所得配合物的潜在生物学应用。所有化合物均由（MO {dollar} rmsb2（Osb2CR）sb2（MeCN）sb6rbracklbrack BFsb4rbracksb2 {dollar}（R = CH {dollar} sb3 {dollar}和CHF {dollar} sb2）{dollar}起始原料合成。 “二聚物三聚物”，{rmal} rm Mosb6（Osb2CCHFsb2）sb {lcub} 12 {rcub}（bpy）sb4 {dollar}（bpy = 2,2 {dollar} spprime {dollar} -bipyridine），三个二核单元通过轴向二氟乙酸桥连接在一起，此外，一种新型的“二聚体”化合物{dol} rmlbrack Mosb4（Osb2CCHFsb2）sb4 {dollar}（1,2-bis（5 {dollar} spprime {dollar }-甲基-2,2 {美元} spprime {美元}-联吡啶-5-基）乙烷} {sb2rbracklbrack BFsb4rbracksb4，{美元}，其中两个双核单元通过赤道键合的四齿螯合配体桥接。相关的双核和聚合产品，{美元} rmlbrack Mosb2（Osb2CCHFsb2）sb2（bpy）sb2（MeCN）（BFsb4）rbracklbrack BFsb4rbrack {美元}和{美元} rmlbrack Mosb4（Osb2CCHFsb2sb4 {bc rcub}，{dollar}有一个已被分离和鉴定。一系列通式为{dol} rmlbrack Mosb2（Osb2CR）sb2 {dollar}（NN）{dol} sb2rbracklbrack {lcub} rm BF {rcub} sb4rbracksb2 {dollar}（NN = bpy， 4,4 {dollar} spprime {dollar} -Me {dollar} sb2 {dollar} bpy，5,5 {dollar} spprime {dollar} -Me {dollar} sb2 {dollar} bpy和1,10-菲咯啉; R = CH {dollar} sb3，{dollar} CHF {dollar} sb2，{dollar}和Ph）被用来探测双核系统的反应性。进行了扩展的Huckel理论计算，以确定双核系统还原后所填充的轨道的性质。这些化合物的浓还原化学是不寻常的，因为观察到四个还原波。确定前两个可逆还原主要是基于配体的过程，但具有30％的金属贡献。制备具有三齿配体1,4,7-三氮杂环壬烷（TACN）和三吡唑基硼酸酯（HB（pz）{dollar} sb3sp-）{dollar}的化合物，并进行晶体学表征。 {dollar} rmlbrack Mosb2（OAc）sb2（TACN）（MeCN）sb2rbracklbrack BFsb4rbracksb2，lbrack Mosb2（OAc）sb2（TACN）（bpy）rbracklbrackbrack BFsb4rbracksb2和lbrack Mosb2（Obbs）（2） rbracklbrack BFsb4rbrack {dollar}代表不常见的四重键合化合物，它们只有一个表面配体。这些配合物是有趣的配位化合物，也可作为双核金属中心与供氮氨基酸侧链相互作用的模型。对于嘌呤核碱基衍生物，9-乙基鸟嘌呤，9-乙基腺嘌呤和1,9-二乙基腺嘌呤，已经观察到不同寻常的配位模式，其中配体通过X6，N7位（X = O，N）桥接双核钼中心。生成的化合物{dollar} rmlbrack Mosb2（Osb2CCHFsb2）sb2 {dollar}（9-EtGH）{dollar} rmsb2（MeCN）sb2rbrack lbrack BFsb4rbracksb2，lbrack Mosb2（Osb2CCHFsb2）rmsb2 {dollar sb2（MeCN）sb2rbracklbrack BFsb4rbracksb2，{dollar}和{dollar} rmlbrack Mosb2（OAc）sb2 {dollar}（1,9- {dollar} rm Etsb2A）sb2rbracklbrack Irbracksb2 {dollar}的特征在于温度1 H NMR，IR和UV可见光谱，以及X射线衍射和元素分析。这些复合物为双核羧酸盐化合物与DNA的潜在体内相互作用提供了模型。

著录项

  • 作者

    Day, Elizabeth Faith.;

  • 作者单位

    Indiana University.;

  • 授予单位 Indiana University.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 1997
  • 页码 191 p.
  • 总页数 191
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;
  • 关键词

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