REDUCED CLUSTERS WITH REMARKABLE TOPOLOGICAL AND ELECTRONIC-PROPERTIES OF THE TYPE OF [V18O42(X)]N-(X=SO4,VO4) WITH TD-SYMMETRY AND RELATED CLUSTERS [V(18-P)AS2PO42(X)]M-(X=SO3,SO4,H2O-P=3,4)

Müller A, DORING J. REDUCED CLUSTERS WITH REMARKABLE TOPOLOGICAL AND ELECTRONIC-PROPERTIES OF THE TYPE OF [V18O42(X)]N-(X=SO4,VO4) WITH TD-SYMMETRY AND RELATED CLUSTERS [V(18-P)AS2PO42(X)]M-(X=SO3,SO4,H2O-P=3,4). ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE. 1991;595(1):251-274.The novel cluster-compounds Na6[V18O42H9(VO4)].21 H2O, (NH4)8[V18O42(SO4)].25 H2O, K6[V15As6O42(H2O)].8 H2O, (NH4)6[V14As8O42(SO3)], (NH4)6[V14As8O42(SO4)] and [N(CH3)4]4[V14As8O42(H2O)] were prepared and characterized by IR- and UV/Vis/NIR-spectroscopy, magnetic measurements and complete crystal structure analysis. For structural data see Inhaltsubersicht. Topological relations to the rhombicuboctahedron spanned by 24 O-atoms of the genuine hypothetical alpha-Keggin ion, at which the square planes are capped by V = O or As2O groups, are discussed. Of particular interest are the "extended" Keggin ions [V18O42(X)]n- (X = SO4, VO4), (formaly derived from the hypothetical genuine alpha-Keggin ion by addition of six V = O groups) which have quite different electron populations in spite of the same structure of their cluster shells

ABOUT [AG(S9)]-, A SYMMETRICAL 10-MEMBERED RING-SYSTEM - PREPARATION, STRUCTURE, AND SPECTROSCOPIC CHARACTERIZATION OF THE SULFUR RICH COMPOUND [(PPH3)2N][AG(S9)].S8

Müller A, Römer M, Bögge H, Krickemeyer E, Zimmermann M. ABOUT [AG(S9)]-, A SYMMETRICAL 10-MEMBERED RING-SYSTEM - PREPARATION, STRUCTURE, AND SPECTROSCOPIC CHARACTERIZATION OF THE SULFUR RICH COMPOUND [(PPH3)2N][AG(S9)].S8. ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE. 1986;534(3):69-76

Cis-/Trans-isomerism of Bis-(trisalkoxy)-hexavanadates - Cis-Na2[V-6(IV)O-7(OH)(6)((OCH2)(3)CCH2OH)(2)) · 8H2O, Cis-(CN3H6)3[V-5(IV)O-V(13)((OCH2)(3)CCH2OH)(2)] · 4,5H2O and trans-(CN3H6)(2)[V-6(V)O-13((OCH2)(3)CCH2OH)(2)] ·H2O

Müller A, Meyer J, Bögge H, Stammler A, Botar A. Cis-/Trans-Isomerie bei Bis-(trisalkoxy)-hexavanadaten - Cis-Na2[V-6(IV)O-7(OH)(6)((OCH2)(3)CCH2OH)(2)) · 8H2O, cis-(CN3H6)3[V-5(IV)O-V(13)((OCH2)(3)CCH2OH)(2)] · 4,5H(2)O und trans-(CN3H6)(2)[V-6(V)O-13((OCH2)(3)CCH2OH)(2)] · H2O. ZEITSCHRIFT FÜR ANORGANISCHE UND ALLGEMEINE CHEMIE. 1995;621(11):1818-1831.Polyoxovanadates with distorted Lindquist-structure, in which six of the twelve mu(2)-oxygen atoms are formally replaced by the oxygen atoms of two coordinated pentaerythritol ligands, can be prepared by a simple method in an aqueous medium. The ''fully reduced'', six-fold protonated compound cis-(Na2V6O7)-O-V(OH)(6){(OCH2)(3)CCH2OH}(2)]. 8H(2)O (1), the mixed valence species cis-(CN3H6)(3)[(VV5O13)-V-IV-O-V{[(OCH2)(3)CCH2OH}(2)]. 4.5H(2)O (2) containing one localized V-IV centre and the ''fully oxidized'' compound trans-(CN3H6)(2)[(V6O13)-O-V{(OCH2)(3)CCH2 . OH}(2)]. H2O (3) have been synthesized and characterized by UV/VIS-, IR- and EPR-spectroscopy, by magnetic measurements, cyclic voltammetry and by a single-crystal X-ray structure analysis. The organic {(CH2)(3)CCH2OH}(3+)-groups tend to cap the triangular faces formed by mu(2)-oxygen atoms of the central approximately octahedral {V6O19}-unit. Therefore the anions of bis-(trisalkoxy)-hexavanadates can exist in a trans-form as well as in an isomeric cis-form referring to a ''basic'' plane of four vanadium atoms of the [V-6]-octahedron. The different relative positions of the ligands have a significant influence on the redox potentials of the compounds. For structural details see ''Inhaltsiibersicht''

New Perspectives in Polyoxometalate Chemistry by isolation of compounds containing very large moieties as transferable building blocks: (NMe4)5[As2Mo8V4AsO40] � 3H2O, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] � 65 H2O, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] � 14 H2O, and (NH4)12[Mo36(NO)4O108(H2O)16] � 33 H2O

Müller A, Krickemeyer E, DILLINGER S, et al. New Perspectives in Polyoxometalate Chemistry by Isolation of Compounds Containing Very Large Moieties as Transferable Building-blocks - (NME4)5[AS2MO8V4ASO40] ·3H2O, (NH4)21[H3MO57V6(NO)6O183(H2O)18] ·65H2O, (NH2ME2)18(NH4)6[MO57V6(NO)6O183(H2O)18] · 14H2O, and (NH4)12[MO36(NO)4O108(H2O)16] · 33H2O. Zeitschrift für anorganische und allgemeine Chemie. 1994;620(4):599-619.The compounds (NMe4)5[As2Mo8V4AsO40] . 3 H2O 2a, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] . 65 H2O 3a, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] . 14 H2O 3b and (NH4)12[Mo36(NO)4O108(H2O)16] . 33 H2O 4a (3a and 4a were not correctly reported in the literature regarding to their composition, structures and the oxidation states of the metal centres) which contain large isolated anionic species, have been prepared (among them 3 a, 3 b, and 4 a in rather high yield) and characterized by complete crystal structure analysis as well as IR/Raman, UV/VIS/NIR, ESR spectroscopy and magnetic susceptibility measurements, redox titrations, bond valence sum calculations, elemental analyses and thermogravimetric studies. Perspectives for polyoxometalate chemistry referring to the synthesis of ''extremely'' large nanoscaled species are discussed, together with the occurrence of a large transferable {Mo17} building block in the compounds 3a, 3b and 4a which also exists in the corresponding iron compound Na3(NH4)12[H15Mo57Fe6(NO)6O183(H2O)18] . 76H2O 7a