Brigitte Eisenmann

A Novel Synthetic Approach to Asymmetric Salen, Dihydrosalen and Tetrahydrosalen Ligands: Structures and O2-Activating Properties of Their Nickel(II) and Cobalt(II) Complexes

A synthetic procedure is described for the preparation of the tetradentate N2O2 ligands H2[H4]L1=6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2-hydroxy-3-t-butyl-5-methyl- phenyl)heptane, H2[H2]L1 = 6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2-hydroxy-3-t-butyl-5-methylphenyl)-1-heptene, and H2L1 = 6-(2-hydroxyphenyl)-2,5-diaza-3,3-dimethyl-1-(2- hydroxy-3-t-butyl-5-methylphenyl)-1,5-heptadiene, which are asymmetric derivatives of the ligands tetrahydrosalen, dihydrosalen, and salen. Complexes Ni[H4]L1, Ni[H2]L1, NiL1, CoL1, Ni[H4]L2 (([H4]L2)2- = anion of H2[H4]L2 = N,N-bis(2-hydroxy-3-t-butyl-5-methylbenzyl)- trans-(S,S)-1,2-diaminocyclohexane), and NiL2 were prepared, characterized (VIS and IR absorption, magnetic moment) and subjected to spectrophotometric titration with pyridine, to determine the equilibrium constants for adduct formation. Single crystal X-ray structure analyses were carried out for Ni[H2]L1 (monoclinic, P21/n; a = 8.926(4), b = 29.324(7), c = 8.411(4) Å; β = 95.3(1)°; Z = 4), CoL1 (monoclinic, C2/c; a = 25.389(2), b = 18.139(2), c = 10.179(1) Å; β = 112.227(6); Z = 8), and Ni[H4]L2·acetone (tetragonal, P41212; a = 13.928(3), c = 33.698(5) Å; Z = 8). In all of the three complexes, the N2O2-metal coordination core is square-planar. The skeleton of the tetradentate ligand is more or less twisted. The planar cobalt(II) complex CoL1 is a low spin d7 system with μexp = 2.02 BM at 298 K, whereas the planar complexes NiL1, Ni[H2]L1 and Ni[H4]L2 are diamagnetic (μexp = 0.28-0.64 BM). The blue solvate Ni[H4]L1- 3EtOH · H2O is paramagnetic (μexp = 3.04 BM), which points to octahedral coordination. In aerated acetone solution, the tetrahydrosalen-type complex Ni[H4]L1 activates dioxygen and one C-N bond is oxidatively dehydrogenated. The VIS spectrum of the dihydrosalen-type complex formed is virtually identical with that of the aldimine complex Ni[H2]L1. In the presence of dioxygen, Co[H4]L1 and Co[H2]L1 are readily oxidized to CoL1 in acetone solution.

Das Zintl-Konzept als Syntheseprinzip: Darstellung und Kristallstrukturen von K2Ba3Sb4 und KBa4Sb3O

Die schwarzen, metallisch glanzenden, sehr hydrolyseempfindlichen Verbindungen K2Ba3Sb4 und KBa4Sb3O wurden aus Schmelzreaktionen, ausgehend von der Stochiometrie entsprechenden Gemengen der Elemente – bei KBa4Sb3O auserdem Sb2O3 – erhalten. K2Ba3Sb4 kristallisiert orthorhombisch in der Raumgruppe Pnma (au200a=u200a870,5(1)u200apm, bu200a=u200a1770,2(2)u200apm, cu200a=u200a923,6(1)u200apm, Zu200a=u200a4) und ist die erste Sb-Verbindung, die in der Anionenteilstruktur ausschlieslich [Sb2]4–-Hanteln aufweist. KBa4Sb3O kristallisiert tetragonal in der Raumgruppeu200aI4/mcm (au200a=u200a882,4(1)u200apm, cu200a=u200a1659,3(2)u200apm, Zu200a=u200a4). In der Anionenteilstruktur bildet Antimon sowohl [Sb2]4–-Hanteln als auch isolierte Sb3–-Ionen. Jedes Antimon-Atom der Hanteln – in K2Ba3Sb4 wie auch in KBa4Sb3O – ist in Form eines zweifach uberkappten trigonalen Prismas koordiniert. Die isolierten Sb3–-Ionen von KBa4Sb3O bilden die Zentren von zweifach uberkappten tetragonalen Antiprismen, die O2–Ionen besetzen Tetraederlucken. n n n nStarting from the Zintl-Concept: Syntheses and Crystal Structures of K2Ba3Sb4 and KBa4Sb3O n n n nThe black, metallic lustrous, air sensitive compounds K2Ba3Sb4 and KBa4Sb3O were prepared from melts of mixtures of the elements, in case of KBa4Sb3O with a stoichiometric amount of Sb2O3. K2Ba3Sb4 crystallizes in the orthorhombic system, space group Pnma (au200a=u200a870.5(1)u200apm, bu200a=u200a1770.2(2)u200apm, cu200a=u200a923.6(1)u200apm, Zu200a=u200a4) and is the first Sb compound with only [Sb2]4– dumbbells in the anionic partial structure. The compound KBa4Sb3O crystallizes in the tetragonal system, space group I4/mcm (au200a=u200a882.4(1)u200apm, cu200a= 1659.4(2)u200apm, Zu200a=u200a4). In this structure antimony forms [Sb2]4–-dumbbells and isolated ions Sb3–. Each antimony ion of the dumbbells – in K2Ba3Sb4 as well as in KBa4Sb3O – is coordinated in form of a bicapped skew trigonal prism. The isolated Sb3– ions in KBa4Sb3O center bicapped tetragonal antiprisms, the O2– ions occupy tetrahedral voids.

Pniktogenidostannate(IV) mit isolierten Tetraeder‐Anionen: Neue Vertreter (E1)4(E2)2[Sn(E15)4] (mit E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) vom Na6[ZnO4]‐Typ und die Überstrukturvariante von K4Sr2[SnAs4]

Die silbrig bis dunkelmetallisch glanzenden Verbindungen (E1)4(E2)2[Sn(E15)4] (E1u200a=u200aNa, K; E2u200a=u200aCa, Sr, Ba; E15u200a=u200aP, As, Sb, Bi) wurden durch Schmelzreaktionen, ausgehend von der Zusammensetzung entsprechenden Gemengen der Elemente erhalten. Sie kristallisieren im Na6[ZnO4]-Typ (hexagonal, Raumgruppe: P63mc, Zu200a=u200a2; Na4Ca2[SnP4]: au200a=u200a938,94(7), cu200a=u200a710,09(8)u200apm; K4Sr2[SnAs4]: au200a=u200a1045,0(2), cu200a=u200a767,0(1)u200apm; K4Ba2[SnP4]: au200a=u200a1029,1(6), cu200a= 780,2(4)u200apm; K4Ba2[SnAs4]: au200a=u200a1051,3(1), cu200a=u200a795,79(7)u200apm; K4Ba2[SnSb4]: au200a=u200a1116,9(2), cu200a=u200a829,2(1)u200apm; K4Ba2[SnBi4]: au200a=u200a1139,5(2), cu200a=u200a832,0(2)u200apm). Die Anionenteilstruktur ist durch isolierte Tetraedereinheiten [Sn(E15)4]8– charakterisiert, die entlang [001] alle gleichsinnig ausgerichtet sind. In der Kationenteilstruktur besetzen Alkali- und Erdalkalimetallkationen eine der beiden Punktlagen gemeinsam, wahrend die zweite nur von Alkalimetallkationen eingenommen wird. Nur K4Sr2[SnAs4] konnte bisher in einer weiteren Modifikation isoliert werden, die eine Uberstrukturvariante mit dreifachem Zellvolumen (hexagonal, Raumgruppe: P63cm, Zu200a=u200a6; au200a=u200a1801,3(2), cu200a=u200a767,00(9)u200apm) und geordneter Kationenteilstruktur darstellt. n n n nPnictogenidostannates(IV) with Discrete Tetrahedral Anions: New Representatives (E1)4(E2)2[Sn(E15)4] (with E1u200a=u200aNa, K; E2u200a=u200aCa, Sr, Ba; E15u200a=u200aP, As, Sb, Bi) of the Na6[ZnO4] Type and the Superstructure Variant of K4Sr2[SnAs4] n n n nThe silvery to dark metallic lustrous compounds (E1)4(E2)2[Sn(E15)4] (E1u200a=u200aNa, K; E2u200a=u200aCa, Sr, Ba; E15u200a=u200aP, As, Sb, Bi) were prepared from melts of stoichiometric mixtures of the elements. They crystallize in the Na6[ZnO4]-type structure (hexagonal, space group: P63mc, Zu200a=u200a2; Na4Ca2[SnP4]: au200a=u200a938.94(7), cu200a=u200a710.09(8)u200apm; K4Sr2[SnAs4]: au200a=u200a1045.0(2), cu200a=u200a767.0(1)u200apm; K4Ba2[SnP4]: au200a=u200a1029.1(6), cu200a= 780.2(4)u200apm; K4Ba2[SnAs4]: au200a=u200a1051.3(1), cu200a=u200a795.79(7)u200apm; K4Ba2[SnSb4]: au200a=u200a1116.9(2), cu200a=u200a829.2(1)u200apm; K4Ba2[SnBi4]: au200a=u200a1139.5(2), cu200a=u200a832.0(2)u200apm). The anionic partial structure consists of tetrahedra [Sn(E15)4]8– orientated all in the same direction along [001]. In the cationic partial structure one of the two cation positions is occupied statistically by alkali and alkaline earth metal atoms. Up to now only for K4Sr2[SnAs4] a second modification could be isolated, forming a superstructure type with three times the unit cell volume (hexagonal, space group: P63cm, Zu200a=u200a6; au200a=u200a1801.3(2), cu200a= 767.00(9)u200apm) and an ordered cationic partial structure.

Na5InTe4 und Na5In2Te6 — Erste Beispiele für Neso-sowie Ditelluro-verbrückte Inotelluroindate/Na5InTe4 and Na5In2Te6 — First Examples of Neso-and Ditelluro-Bridged Inotelluroindates

Abstract Single crystals of the ternary com pounds Na5InTe4 and Na5In2Te6 have been grown from the melt und have been investigated by X-ray single crystal techniques. Na5InTe4: orthorhombic, space group Pbcn; Z = 8; a = 742.7(4) pm, b = 2015.4(8) pm, c = 1773.3(6) pm; Na5In:Te6: orthorhombic, space group Cmc21; Z = 8; a = 902.1(4) pm, b = 1536.1(5) pm , c = 2356.5(6) pm. The crystal structure of Na5InTe4 contains isolated InTe4 tetrahedra (mean bond length: 278.8 pm). In the crystal structure of Na5In2Te6 InTe4 tetrahedra are connected through common vertices to Zweiereinfach-chains. Two neighbouring chains each are joined further to ribbons through Te -Te bridges between every second InTe4 tetrahedron.

Na2[SnAs2], die erste Zintl-Phase mit einem [SnAs2]-Raumnetz aus adamantan-analogen [Sn4As10]-Einheiten / Na2[SnAs2], the First Zintl Phase with a [SnAs2] Framework Based on Adamantan Analogous [Sn4As10] Units

The metallic grey compound Na2[SnAs2] was prepared from a molten mixture of the elements. Na2[SnAs2] crystallizes in the tetragonal space group I41/acd, Z = 32, with the lattice constants: a = 1416.6(3) pm, c = 2119.1(4) pm, c/a = 1.4959. In the crystal structure four [SnAs4] tetrahedra are connected by common corners forming adamantan analogous [Sn4As10] units. The further connection of these tetrameric moieties by the terminal As atoms results in a three-dimensional framework ∞3[SnAs22-], in which the Na atoms occupy distorted tetrahedral and octahedral holes.

[K(222-crypt)]2TeSe10 und [Ba(222-crypt)(en)]TeSe10·en0,5: Verbindungen mit einem neuen spirozyklischen TeSe102--Polychalkogenid-Anion / [K(222-crypt)]2TeSe10 and [Ba(222-crypt)(en)]TeSe10 · en0.5: Compounds with a New Spirocyclic Polychalcogenide Anion TeSe102-

Attempts to prepare selenotellurates with coordination numbers greater than three for the tellurium atom led to the title compounds [K(222-crypt)]2TeSe10 and [Ba(222-crypt)(en)]TeSe10·en0.5 with a new mixed polychalcogenide anion TeSe102-. The crystal structures of both compounds contain four-coordinate tellurium with two bidentate Se5 forming a spirocyclic arrangement with Te as the common spiro atom in a planar, almost square coordination. The potassium cation is cryptated by the macro-bicyclic aminopolyether 222-crypt (CN 8), whereas the barium cation is coordinated by the cryptand and a further solvate molecule of ethylenediamine, resulting in a total coordination number of 10. [K(222-crypt)]2TeSe10: PI, a = 1333.3(6) pm, b = 1214.6(6) pm, c = 1078.3(4) pm, α = 95.80(6)°, β = 90.18(6)°, γ = 115.20(6)°, R = 0.073; [Ba(222-crypt)(en)]TeSe10 · en0.5: PĪ, a = 1802.2(6) pm, b = 1132.1(4) pm, c = 1049.4(4) pm, α = 79.80(6)°, β = 87.27(6)°, γ = 84.63(6)°, R = 0.076.

Cyclische Phosphidostannat(III)-Anionen [Sn12P24]36– in Sr3[Sn2P4]

Die metallisch glanzende, sehr hydrolyseempfindliche Verbindung Sr3[Sn2P4] wurde aus Schmelzreaktionen, ausgehend von der Stochiometrie entsprechenden Gemengen der Elemente erhalten. Sr3[Sn2P4] kristallisiert orthorhombisch in der Raumgruppe Cmca (au200a=u200a2510,4(9), bu200a=u200a1259,3(6), cu200a=u200a1869,3(8), Zu200a=u200a24). In der Anionenteilstruktur sind sechs zu Si2Cl6 isostrukturelle Baugruppen [Sn2P6] uber jeweils vier gemeinsame P-Liganden zu Ringeinheiten [Sn12P24]36– verknupft. Die Strontium-Kationen sind verzerrt oktaedrisch von P umgeben. Die Atomanordnung last sich als verzerrte kubisch dichteste Packung von P3–-Ionen auffassen, in der geordnet 3/4 der Oktaederlucken durch Sr2+ und 1/4 durch Sn2-Hanteln besetzt sind. n n n nCyclic Phosphidostannate(III) Anions [Sn12P24]36– in Sr3[Sn2P4] n n n nThe metallic lustrous, air sensitive compound Sr3[Sn2P4] was prepared from melts of mixtures of the elements. Sr3[Sn2P4] crystallizes in the orthorhombic system, space group Cmca (au200a=u200a2510,4(9), bu200a=u200a1259,3(6), cu200a=u200a1869,3(8), Zu200a=u200a24). In the anionic partial structure six moieties [Sn2P6] isostructural to Si2Cl6 are linked by each four common P-ligands forming cyclic units [Sn12P24]36–. The strontium cations are octahedrally coordinated by P. The arrangement can be described as a distorted cubic close packing of P3– in which in an ordered manner 3/4 of the octahedral vacancies are occupied by Sr2+ and 1/4 by Sn2-dumbbells.

A tin-119 Mössbauer spectroscopic investigation of some chalcogen-containing Zintl phases

Abstract The 119Sn Mossbauer parameters for some chalcogen-containing Zintl phases of composition M4SnX4 (M=Na, K; X=S, Se, Te), Na2SnSe3, M3SnTe3 (M=K, Rb, Cs), Cs4Sn2Te7 and M2SnTe5 (M=K, Rb) are reported. All the compounds contain tetrahedrally coordinated tin and the chemical isomer shift data show the tin to be involved in covalent bonding with the chalcogen atoms. The dependence of the 119Sn Mossbauer parameters on the local coordination of tin, the extent of polymerisation of the anionic sub units, the transfer of electrons from the alkali metal to the anionic units, and the electronegativity of the chalcogen atoms are discussed.

Dimere und polymere Pnictidostannat(IV)-Anionen -Darstellung und Kristallstrukturen von Na2K3[SnP3], Na2Cs3[SnP3] und Na2K3[SnBi3] / Dimeric and Polymeric Pnictidostannate(IV) Anions -Preparation and Crystal Structures of Na2K3[SnP3], Na2Cs3[SnP3] and Na2K3[SnBi3]

Abstract The metallic lustrous compounds Na2K3[SnP3], Na2Cs3[SnP3], and Na2K3[SnBi3] were prepared from melts of mixtures of the elements. The isotypic compounds Na2K3[SnP3] and Na2Cs3[SnP3] crystallize in the orthorhombic system, space group Cmca (No 64), Z = 8, with lattice constants a = 1996.1 (4)/2047.9(4) pm, b = 669.5(1)/686.5(2) pm, c = 1494.5(2)/1617.8(3) pm. The structure is characterized by dimeric units [Sn2P6] 10- of edge-sharing [SnP4] tetrahedra, which are coordinated by the alkali cations. Na2K3[SnBi3] crystallizes in the orthorhombic system, space group Ibca (No 73), Z = 8, with lattice constants a = 718.2(1) pm , b -1692.6(2) pm, c = 2159.5(2) pm. In the anionic partial structure [SnBi4] tetrahedra are connected via common corners to infinite 1∞[SnBi3]5- Zweier single chains. The sodium and potassium cat ions separate the chains from each other. Neglecting the distortions caused by covalent bonding and different radii both structure types can be classified as superstructure defect variants of the Li3Bi structure. Different orderings in the occupation of the tetrahedral voids lead to the variants in the anionic assemblies.

Oligomere Tetraeder-Anionen in Borophosphaten: Darstellung und Kristall­strukturen von NaFe[BP2O7(OH)3] und K2Fe2[B2P4O16(OH)2 ]/Oligomeric Tetrahedral Anions in Borophosphates: Synthesis and Crystal Structures of NaFe[BP2O7(OH)3] and K2Fe2[B2P4O16(OH)2]

Abstract Crystals of the title compounds were grown under hydrothermal conditions. The crystal structures were determined by single crystal data. NaFe[BP2O7(OH)3] (monoclinic, C 2/c, a = 1042.0(2), b = 821.5(1), c = 921.7(1) pm, β = 116.60(1)°, Z=4): The crystal structure contains isolated anions [BP2O7(OH)3]4-, which correspond to trinuclear units PO1/2O3-BO2/2(OH)2 -PO1/2O2(OH) of corner sharing tetrahedra. Fe3+ is coordinated octahedrally by oxygen, Na+ is 8 -fold coordinated by oxygen forming cubes. K2Fe2[B2P4O16(OH)2] (triclinic, P1̄, a = 516.7(1), b = 808.9(1), c = 834.0(1) pm, α = 87.06(f), β = 80.21(1), γ = 86.59(1)°, Z = 1): The crystal structure contains isolated anions [B2P4O16(OH)2]8-. Four-membered rings of tetrahedra with two additional terminal phosphate groups are formed by condensation of two trinuclear units P O1/2O3 -BO3/2(OH) -PO2/2O2. Fe3+ is in an octahedral and K+ in an irregularly 10-fold coordination by oxygen.