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Title: Synthesis and characterization of building blocks and polynuclear complexes of ruthenium, osmium and manganese
Other Titles: Han liao, e he meng de zu zhuang ji yuan ji duo he pei he wu de he cheng yu biao zheng
含釕, 鋨和錳的組裝基元及多核配合物的合成與表徵
Authors: Guo, Junfang (郭俊芳)
Department: Department of Biology and Chemistry
Degree: Doctor of Philosophy
Issue Date: 2008
Publisher: City University of Hong Kong
Subjects: Complex compounds -- Synthesis.
Complex compounds -- Characterization.
Notes: CityU Call Number: QD474 .G86 2008
xxii, 244 leaves : ill. 30 cm.
Thesis (Ph.D.)--City University of Hong Kong, 2008.
Includes bibliographical references (leaves 213-235)
Type: thesis
Abstract: This thesis is divided into two parts. In part one, a number of ruthenium and osmium cyano building blocks have been synthesized and characterized. Two new dicyanoruthenium complexes containing picolinic acid (Hpic), trans-(PPh4)2[RuII(pic)2(CN)2] and trans-(PPh4)[RuIII(pic)2(CN)2], have been synthesized and characterized by IR, ESI-MS, UV-Vis, elemental analysis, and X-ray crystallography. A series of dicyanoosmium(III) complexes, trans-(PPh4)[OsIII(3,3´-X2,5,5´- Y2-salchda-CN)(CN)2], and another series of dicyanoosmium(IV) complexes, trans-(PPh4)[OsIV(3,3´-X2,5,5´-Y2-salchda-O)(CN)2] (H2(salchda) = N,N´-bis- (salicylidene)-o-cyclohexyldiamine, X = H, Br, Cl, Y = H, Br, Cl, CH3, CH3O, tBu), have been synthesized and characterized by IR, ESI-MS, UV-Vis, elemental analysis. The structures of trans-(Ph4P)[OsIII(salchda-CN)(CN)2] and trans-(PPh4)[OsIV(salchda-O)(CN)2] have been determined by X-ray crystallography. In the second part, a number of polynuclear compounds containing RuIII, OsIII and MnV have been synthesized and structurally characterized. A number of novel 3d-4d, 3d-5d compounds have been prepared from the dicyanoruthenium(III) and dicyanoosmium(III) complexes, trans-[RuIII(acac)2(CN)2]- (Hacac = acetylacetone), trans-[RuIII(salen)(CN)2]- (salen2- = N,N´-bis(salicylidene)-o-ethyldiamine dianions), trans- [OsIII(salen)(CN)2]- and trans-[OsIII(salchda-CN)(CN)2]-. These building blocks are combined with 3d ions to produce polynuclear complexes. [Ni(tren)][RuIII(acac)2(CN)2](ClO4)⋅CH3OH (tren = tris(2-aminoethyl)amine), [Ni(tren)][Ru(salen)(CN)2](ClO4)⋅H2O, [Ni(tren)][Os(salen)(CN)2](ClO4), [Ni(cyclen)][Ru(acac)2(CN)2](ClO4)⋅CH3OH (cyclen = 1,4,7,10-tetraazacyclododecane) and [Os(salen)(CN)2][Cu(Me3tacn)]·ClO4 (Me3tacn = 1,4,7-Trimethyl-1,4,7-triazacyclononane) have a one-dimensional zig-zag chain structure. While [Os(salen)(CN)2]2[Cu(Me3tacn)]·CH3OH exists as a 1-D neutral zig-zag or herring-bone-like polymer. [Fe(salen)][Ru(acac)2(CN)2] and the homonuclear polymer {[Os(salen)(CN)]·0.5H2O}n are also neutral but have a one-dimensional linear chain structure. On the other hand, {[Mn(5,5´-Me2salen)]2[Ru(acac)2(CN)2]}·[Ru(acac)2(CN)2]·2CH3OH (5,5΄-Me2salen = N,N´-bis(5,5΄-dimethylsalicylidene)o-ethylenediimine) is a trinuclear complex, but has a one-dimensional linear chain structure composed of trinuclear units linked by π-π stacking. [Mn(DMF)4][Os(salchda-CN)(CN)2]2·4CH3OH is a trinuclear complex. [Ni(tren)][RuIII(acac)2(CN)2](ClO4)⋅CH3OH and [Ni(tren)][Ru(salen)(CN)2](ClO4)⋅H2O exhibit ferromagnetic coupling between Ru(III) and Ni(II) metal centers. On the other hand, [Ni(tren)] [Os(salen)(CN)2](ClO4) is a metamagnet at about 3 K. The magnetic measurement of {[Mn(5,5´-Me2salen)]2[Ru(acac)2(CN)2]}·[Ru(acac)2(CN)2]·2CH3OH shows that it is a single molecule magnet. Three bimetallic coordination polymers constructed from [Mn(N)(CN)4]2-, {[Ni(cyclen)][Mn(N)(CN)4]·CH3OH}n, {[Cu(cyclen)][Mn(N)(CN)4]}n, {[Mn(5,5΄-Me2salen)]2[Mn(N)(CN)4]·CH3OH}n have been synthesized and structurally characterized. The former two compounds have one-dimensional zig-zag chain structures; while the third one has a two-dimensional sheet-like network structure. Magnetic studies of these compounds show that there is no significant magnetic coupling between the paramagnetic metal centers. Treatment [Mn(N)(CN)4]2- with 2,2´-bipydine (bpy), 1,10-phenanthroline (phen), ethylenediamine (en) and 1,2-diaminopropane (pn) in methanol produced a series of tricyanonitridomanganate(V) (PPh4)[MnN(L)(CN)3] (L = bpy, phen, en and pn). These complexes have been structurally characterized.
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