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Direct thermally induced reactions between rare earth metals (Ln = Y,Ce, Dy, Ho, and Er) activated by Hg metal and 3,5-diphenylpyrazole (Ph(2)pzH) or 3,5-di-tert-butylpyrazole (tBu(2)pzH) yielded either homoleptic complexes [Ln(n)(R(2)pz)(3n)] or a heteroleptic complex [Ln(Ph(2)pz)(3)(Ph(2)pzH)(2)] From Ph(2)pzH, [Ce-3(Ph(2)pz)(9)], [Dy-2(Ph(2)pz)(6)], [Ho-2(Ph(2)pz)(6)], and [Y(Ph(2)pz)(3)(Ph(2)pzH)(2)] were isolated. The first has a bowed trinuclear Ce-3 backbone with two eta(2) pyrazolate ligands on the terminal metal atoms and one on the middle, and bridging by both mu-eta(2):eta(2) and mu-eta(2):eta(5) ligands between the terminal and the central Ce atoms. Although both the Dy and Ho complexes are dinuclear, the former has the rare mu-eta(2):eta(1) bridging whilst the latter has mu-eta(2):eta(2) bridging. Thus the dysprosium complex is seven-coordinate and the holmium is eight-coordinate, in contrast to any correlation with Ln(3+) ionic radii, and the series has a remarkable structural discontinuity. The heteroleptic Y complex is eight coordinate with three chelating Ph(2)pz and two transoid unidentate Ph(2)pzH ligands. From tBu(2)pzH, dimeric [Ln(2)(tBu(2)pz)(4)] (Ln = Ce, Er) were isolated and are isomorphous with eight coordinate Ln atoms ligated by two chelating terminal tBu(2)pz and two mu-eta(2):eta(2) tBu(2)pz donor groups. They are also isomorphous with previously reported La, Nd, Yb, and Lu complexes.

Reaction of LnCl3 with Na2(PDDA) (PDDA = phenylene-1, 2-dioxydiacetate) in a 1 to 2 mol ratio in aqueous solution yielded [Ln2(PDDA)3(H2O)6]•2H2O, structurally characterized for Ln = Ce (1), Sm (2) (redetermination), Tb (3) and Y (4) in a monoclinic C2/c array, a second related structural form [orthorhombic, Pbcn] being obtained for Tb (5), Ho (6) and Er (7). The 'domains of existence' of these two previously described forms are now extended to Ce–Dy, Y, and Eu–Er, respectively. Reaction under the same conditions for the heavier Yb3+ ion yielded [Yb2(PDDA)3(H2O)6](∞|∞)•4H2O (8), orthorhombic, Pbca. In the case of Ln = La the bimetallic species [NaLa(PDDA)2(H2O)2](∞|∞)•4H2O (9) was obtained, while reaction of LnCl3 with Na2(PDDA) in a 1 to 3 mol ratio led to the isolation of the isotypic (monoclinic, P21/c) [NaLn(PDDA)2(H2O)2](∞|∞)•4H2O) for Ln = Ce (10) and Sm (12). With the smaller Ln = Yb, the more definitively bimetallic [NaYb(PDDA)2(H2O)2](∞|∞)•3H2O (13) (triclinic, Pequation image)) was obtained, the trihydrate solvation ascribed differing from that recorded (dihydrate) in a cosynchronous report.

A series of heterobimetallic complexes [RE₂Ca(OQ)₈]·nHOQ(RE = Sm, Gd, Tb, Ho, Tm, Yb, Lu, Y, Sc) and the isostructural [Gd₂Mg(OQ)₈] were synthesised and structurally characterised. They were mainly obtained after direct reactions of the elemental rare earth metals with calcium metal in the presence of 8-hydroxyquinoline (HOQ) and a 1, 3, 5-tri-tert-butyl-benzene (tBuB) flux, and some complexes were synthesised by pseudo solid-state rearrangement reactions between powdered RE(OQ)₃ and AE(OQ)₂ (AE = Mg, Ca) in a 1, 2, 4, 5-tetramethylbenzene (TMB) flux, at elevated temperatures. The linear trinuclear [RE₂Ca(OQ)₈] moieties show a six-coordinate central calcium atom flanked by two eight-coordinate rare earth atoms surrounded by six chelating-bridging OQ and two terminal chelating OQ ligands. The structurally novel [Sc₂Ca(OQ)₈] has a bent Sc-Ca-Sc backbone and exhibits an eight-coordinate central calcium and two seven-coordinate scandium ions.

Mixed carboxylate complexes of cerium(III) and yttrium(III), [Ce2(OAc)4(salH)2(OH2)4]·4HOAc and [Y2(OAc)4(salH)2(OH2)4]·2H2sal (HOAc, H2sal ≡ acetic, salicylic acids) have been structurally characterized as tetrakis(acetic) and bis(salicylic) acid solvates, respectively. The dinuclear complex components take an identical form: [(OAc-O,O')(H2O)2Ln(O,μ-O'-OAc)2(O-Hsal-O')2Ln(OH2)2(O,O'-OAc)], with bridging pairs of acetate and salicylate ligands. The solvating acid molecules are closely and elegantly associated with the dinuclear complex via hydrogen bonding, these aggregates in turn being held together in the lattice by interactions between water molecule hydrogen atoms and neighboring carboxylate oxygen atoms.

Monomeric manganese(II) complexes of bulky alkyl/ aryl-substituted phenoxides, [Mn{C6HnRmO}2(DME)] [1: R = C6H5, n = 3, m = 2 (2,6); 2: R = Me3C, n = 3, m = 2 (2,6); 3: R = Me3C, n = 2, m = 3 (2,4,6)] were prepared in yields of 37, 44 and 72 %, respectively, from the reaction of manganese powder, Hg(C6F5)2 and the corresponding phenol in the presence of a little mercury in dimethoxyethane (DME). The compounds were characterized spectroscopically and by magnetic measurements. The single crystal structures of 1 and 3 and also of the mixed phenoxide complex [Mn{(C6H3(C6H5)2-2,6-O}{C6H3(Me3C)2-2,6-O}(DME)] 4 are reported.

Reaction of the commercially available potassium 1,2-benzenedisulfonate (K2L) with calcium chloride, strontium nitrate, and barium chloride in aqueous solution yielded [Ca2L2(H2O)4], [Sr4L4(H2O)8]·1.5H2O and [Ba2L2(H2O)5]·H2O in a form suitable for single-crystal X-ray determination. From one preparation of the calcium complex a few crystals of [K2CaL2(H2O)3]·0.5H2O were obtained but were not representative of the bulk product. From reaction of CaCO3 with H2L and recrystallization from aqueous ethanol, crystals of [Ca2L2(H2O)6]·EtOH deposited. All complexes are coordination polymers with metal atoms being bridged and chelated by 1,2-benzenedisulfonate groups, which show an enormous variety of coordination modes, and coordinated by water molecules, some of which are bridging. Calcium has an eight-coordinate ion in all compounds, potassium six-coordinate in the bimetallic complex; the strontium complex has eight- and nine-coordinate strontium atoms and the barium complex nine- and eleven-coordinate barium atoms.

The preparations and characterisations of a range of lanthanoid 4-(R)-substituted (4-Rcinn, R = OH, OMe, NO2, Cl), known to have good anticorrosion properties, are reported. The crystal structure of [Ce(4-OHcinn)3(MeOH)2(H2O)]·MeOH is a polymer, in which the cerium atoms are nonacoordinate, and adjacent cerium atoms are bridged by either two bridging bidentate or two bridging tridentate carboxylate ligands. Each cerium atom also has one monodentate 4-hydroxycinnamate ligand, one aqua ligand, and two methanol ligands.

Anhydrous rare earth tris(cinnamates) [RE(cinn)3] (RE = La–Lu, Y and Sc and cinnH = trans-cinnamic acid) were prepared by metathesis in water and by direct reaction of the metal with cinnamic acid in a 1,2,4,5-tetramethylbenzene flux at ca. 200 °C. X-ray crystal structure determinations and X-ray powder data show that, in the solid state, the larger lanthanoids (La–Dy) form an isomorphous polymeric series consisting of homoleptic nine-coordinate metal centres bonded to three chelating and bridging tridentate cinnamates. The late REIII cinnamate (RE = Dy, Ho–Lu, Y) complexes also form linear one-dimensional polymeric chains with all RE metal atoms being seven-coordinate. The cinnamates are either bound tridentate bridging in a μ-η2:η1 fashion, or μ-η1:η1syn-syn bidentate bridging. A structural break occurs at dysprosium which has been characterised in both crystallographic forms, and gives solely the late RE form when precipitated at 80 °C. ScIII cinnamate was also isolated as an analytically pure precipitate which was, again, found to be anhydrous in nature. A structural change was identified by powder XRD between the late REIII cinnamates and ScIII cinnamate.

The ligand N,N-dimethyl(N′-trimethylsilyl)ethane-1,2-diamine (HL) was treated with ZnEt2 in varying stoichiometric ratios to synthesize [EtZnL]2 and [ZnL2] complexes. Crystal data: [EtZnL]2, monoclinic, P21/n, a = 10.0149(5) A, b = 8.0296(3) A, c = 16.1689(8) A, β = 91.715(2)°. [ZnL2], monoclinic, P21/n, a = 8.8457(3) A, b = 15.4249(6) A, c = 16.0121(7) A, β = 92.656(1)°. The former complex is an amido nitrogen bridged dimer with distorted tetrahedral stereochemistry of the zinc atom and the latter is a distorted tetrahedral monomer based on amide/amine chelation.

Reaction of 8-hydroxyquinoline (HOQ) with holmium metal in the presence strontium metal and metallic mercury at 190 °C under vacuum in a 1,3,5-tri-tert-butylbenzene flux yielded (η2-8-quinolinolato-κ:N,O(Ho(2))bis(η2-8-quinolinolato-κ:N,O(Ho(1)))hexakis(μ-(O)-8-quinolinolato-κ:N,O(Ho(1))trisholmium(III) as an 8-hydroxyquinoline solvate (1) (C2/c, a = 17.336(4) A, b = 23.464(5), c = 18.038(4) A, β = 92.92(3)°, V = 7328(3) A3, R1 = 0.0622). The complex was resynthesised after preactivation of the metals by mercury and then heating them with HOQ at 190 °C.

From a range of preparative methods, three geometric isomers of bis(diphenylarsino)methane-dichloroplatinum(II) have been isolated, viz. cis-PtCl2(dpam), trans, trans-Pt2Cl4(dpam)2 and cis, trans-Pt2Cl4(dpam)2. Their structures were determined by single-crystal X-ray diffraction. Strukturisomere von Bis(diphenylarsino)methan-dichloroplatin(II) Mit Hilfe einer Reihe praparativer Verfahren wurden drei geometrische Isomere von Bis(diphenylarsino)methan-dichloroplatin(II) isoliert: cis-PtCl2(dpam), trans, trans-Pt2Cl4(dpam)2 und cis, trans-Pt2Cl4(dpam)2, und ihre Strukturen durch Einkristall-Rontgenstrukturanalyse bestimmt.

Reaction of CeCl3·7H2O with Na2(oda) (oda = O(CH2CO2)22— oxydiacetate) in a 2:3 ratio gives the neutral cerium(III) complex [Ce2(oda)3(H2O)3]·9H2O (1). Treatment of a 1:3 mixture of CeCl3·7H2O and H2oda in water with 4 molar equivalents of NaOH also gives 1 but, with a larger excess of NaOH, the tri-sodium salt Na3[Ce(oda)3]·9H2O (2) is isolated. Formation of a tri-ammonium analogue of 2 can be achieved by neutralisation of an aqueous solution of CeCl3·7H2O and H2(oda) in a 1:3 ratio by NH4OH, giving (NH4)3[Ce(oda)3]·7H2O (3). Use of the cerium(IV) reagent (NH4)2[Ce(NO3)6] with Na2(oda) results in reduction to cerium(III) under ambient conditions and isolation of 1. However, in the absence of light this reaction yields crystals of the novel cerium(IV) heterobimetallic [Ce(oda)3Na4(NO3)2] (4). Each of these complexes exhibit a 3-D network structure having a common nine-coordinate [Ce(oda)3]n— (n = 2 or 3) subunit, irrespective of the oxidation state of cerium. In 1, six [Ce(oda)3]3— anions are connected, through bridging bidentate carboxylates, to a second Ce3+ site further coordinated by three water molecules. In contrast, the ammonium salt 2, displays isolated [Ce(oda)3]3— anions, devoid of further carboxylate bonding, but enmeshed within a network of hydrogen-bonded NH4+ cations and water molecules. The remarkable structure of 4 consists of infinite 2-D sheets of [Na2(NO3)]+ pillared by [Ce(oda)3]2— units, the connectivity arising by multidentate nitrate and carboxylate bridging. Bildung von Netzwerkstrukturen bei Oxydiacetaten mit CeIII und CeIV Die Umsetzung von CeCl3·7H2O mit Na2(oda) (oda = O(CH2CO2)22—, Oxydiacetat) im Verhaltnis 2:3 fuhrt zu dem neutralen Cer(III)-Komplex [Ce2(oda)3(H2O)3]·9H2O (1). Auch bei der Umsetzung einer 1:3-Mischung von CeCl3·7H2O mit H2(oda) in Wasser mit 4 Aquivalenten NaOH bildet sich 1, mit einem groseren Uberschus an NaOH isoliert man jedoch das Trinatriumsalz Na3[Ce(oda)3]·9H2O (2). Das analoge Triammonium-Salz, (NH4)3[Ce(oda)3]·7H2O (3), erhalt man durch Neutralisation einer wassrigen Losung von CeCl3·7H2O und H2(oda) (molares Verhaltnis 1:3) mit NH4OH. Setzt man das Cer(IV)-Reagens (NH4)2[Ce(NO3)6] zusammen mit Na2(oda) ein, so beobachtet man unter normalen Bedingungen Reduktion zu CeIII und isoliert 1. Allerdings erhalt man in Abwesenheit von Licht Kristalle der neuartigen hetero-bimetallischen CeIV-Verbindung [Ce4(oda)3Na4(NO3)2] (4). Samtliche Komplexe bilden dreidimensionale Netzwerkstrukturen und enthalten als strukturbestimmende Einheit die Anionen [Ce(oda)3]n— (n = 2 oder 3), in denen Cer unabhangig von seiner Oxidationsstufe stets die Koordinationszahl 9 aufweist. In 1 werden sechs [Ce(oda)3]3—-Anionen uber zweizahnige Carboxylat-Liganden mit weiteren Ce3+-Ionen verknupft, deren Koordinationssphare durch drei Wassermolekule aufgefullt wird. Im Gegensatz hierzu enthalt die Ammoniumverbindung 2 isolierte [Ce(oda)3]3—-Anionen, eingebettet in ein Netzwerk von Wasserstoffbrucken, an denen NH4+-Ionen und Wassermolekule beteiligt sind. Die bemerkenswerte Struktur von 4 besteht aus unendlichen zweidimensionalen, kationischen Schichten der Zusammensetzung [Na2(NO3]+ , zwischen die saulenformige [Ce(oda)3]2—-Einheiten eingelagert sind; die Verknupfung wird durch mehrzahnige Nitrat-Ionen und verbruckende Carboxylat-Liganden bewerkstelligt.

NdCl3(dme)2 is a chloride bridged dimer [NdCl2(μ-Cl)(dme)2]2, the first example of this structural type in the LnCl3(dme)n system, whereas YbCl3(thf)3.5 has the structure [YbCl2(thf)5][YbCl4(thf)2], thereby extending this arrangement with a seven coordinate cation to an element previously giving only six coordinate LnCl3(thf)ncomplexes. Neue Variationen zum Strukturthema LnCl3(L)n (L = Tetrahydrofuran oder 1, 2-Dimethoxyethan) — NdCl3(dme)2 und YbCl3(thf)3, 5 Das uber Chlorobrucken dimerisierte [NdCl2(μ-Cl)(dme)2]2 ist das erste Beispiel dieses Strukturtyps im LnCl3(dme)n-System. Dagegen hat YbCl3(thf)3, 5 die ionische Struktur [YbCl2(thf)5][YbCl4(thf)2] mit siebenfach koordiniertem Ytterbium-Atom des Kations, was die Kenntnis der bisher bei Komplexen [LnCl3(thf)n] nur bekannten Koordinationszahl sechs erweitert.

Reactions of PtCl2(cod) (cod = cycloocta-1,5-diene) with 2,4,6-trifluoro- and 2,3,4,5-tetrafluoro-phenyllithium in diethyl ether gives Pt(C6H2F3-2,4,6)2(cod) (1) (monoclinic, P21/n, Z = 4, a = 7.141(1), b = 15.002(2), c = 17.071(3) A, β = 91.37(2)°) and Pt(C6HF4-2,3,4,5)2(cod) (2) (triclinic, P 1, Z = 2, a = 10.150(2), b = 10.762(2), c = 10.812(2) A, α = 63.606(3), β = 63.327(3), γ = 76.496(3)°) respectively, which have two ipso carbon atoms and two double bond midpoint centres in a square planar arrangement, and aromatic rings angled near perpendicular to the coordination plane. Zwei Platindien-Synthesereagentien Pt(C6H2F3-2,4,6)2(cod) und Pt(C6HF4-2,3,4,5)2(cod) Die Umsetzungen von PtCl2(cod) (cod = cycloocta-1,5-dien) mit 2,4,6-Trifluoro- bzw. 2,3,4,5Tetrafluoro-phenyllithium in Diethylether fuhrt zu Pt(C6H2F3-2,4,6)2(cod) (1) (monoklin, P21/n, Z = 4, a = 7,141(1), b = 15,002(2), c = 17,071(3) A, β = 91,37(2)°) und Pt(C6HF4-2,3,4,5)2(cod) (2) (triklin, P 1, Z = 2, a = 10,150(2), b = 10,762(2), c = 10,812(2) A, α = 63,606(3), β = 63,327(3), γ = 76,496(3)°). In beiden Strukturen liegt eine quadratisch-planare Koordination mit zwei ipso-Kohlenstoffatomen und zwei Mittelpunkten von Doppelbindungen vor. Die aromatischen Ringe stehen nahezu senkrecht auf der Koordinationsebene.

Oxidation of [Yb(OArR)2(THF)3] (OArR = OC6H2–2,6-tBu2-4-R; R = H, Me, tBu) with HgX2 or with (CH2X)2 (X = Cl, Br, I) in THF yields [Yb(OArR)2X(THF)2], whilst [Yb(OArMe)2Cl(THF)2] was also obtained by oxidation of the appropriate Yb(II) aryloxide with C2Cl6 in THF. An X-ray crystal structure determination has shown [Yb(OArMe)2I(THF)2] to be a five coordinate monomer, in which ytterbium has distorted square pyramidal stereochemistry with mutually trans OArMe and THF ligands in the square plane and an apical iodide. Attempts to grow single crystals of [Yb(OArH)2Cl(THF)2] yielded [Yb(OArH)2OH(THF)]2, shown to be an hydroxo-bridged dimer with five-coordinate ytterbium by X-ray crystallography. Organoamido- und Aryloxo-Lanthanoide. 26 Synthese von Bis(aryloxo)halogenoytterbium(III)-Komplexen: [Yb(OAr)2X(THF)2] (X = Cl, Br, I, OAr = OC6H2–2,6-tBu2-4-R; R = H, Me, tBu) und die Kristallstrukturen von [Yb(OC6H2-2,6-tBu2-4-Me)2I(THF)2] und [Yb(OC6H3-2,6-tBu2)2OH(THF)]2 Die Umsetzung von [Yb(OArR)2(THF)3] (OArR = OC6H2-2,6-tBu2-4-R; R = H, Me, tBu) mit HgX2 (X = Cl, Br, I) oder mit (CH2X)2 in THF fuhrt zu [Yb(OArR)2X(THF)2]. [Yb(OArMe)2Cl(THF)2] ist ebenso durch Oxidation des entsprechenden Yb(II)-Aryloxides mit C2Cl6 in THF erhaltlich. Nach Auskunft einer Einkristallstrukturanalyse liegt [Yb(OArMe)2I(THF)2] als Monomer mit funffach koordiniertem Ytterbium vor. Die Anordnung der Liganden um das Ytterbiumatom entspricht einer verzerrten quadratischen Pyramide, mit trans-standigen OArMe- und THF-Liganden in der Basisflache und dem Iod-Atom in der apikalen Position. Versuche, Einkristalle von [Yb(OArH)2Cl(THF)2] zu zuchten, fuhrten zur Bildung von [Yb(OArH)2OH(THF)]2, in denen eine OH-verbruckte dimere Einheit vorliegt, so dass Ytterbium ebenfalls die Koordinationszahl 5 erreicht.

Black single crystals of [Lu(Db18c6)(H2O)3(thf)6]4(I3)2(I5)6(I8)(I12) were obtained from lutetium, I2 and Db18c6 (dibenzo-18-crown-6) in THF solution. In the bulky cation, Lu3+ is surrounded by nine oxygen atoms, six of Db18c6 and three of water molecules to which two THF molecules are attached each. Meanwhile, four polyiodide anions, (I3)–, (I5)–, (I8)2– and (I12)2–, in a 2:6:1:1 ratio form a three-dimensional network and leave space for the bulky cations.

The barium perfluoroalkanedisulfonates Ba(O3S)2(CF2)n (n = 1, 3–5) and the new potassium fluoroalkanedisulfonates K2(O3S)2CHF, K2(O3S)2CF2, and K2(O3S)2(CF2)5 have been prepared by reaction of (CF2)n(SO2F)2 (n = 1, 3–5) or CHF(SO2F)2 with CaO (or Ca(OH)2) and M(OH)x (M = Ba, x = 2; M = K, x = 1) or with Ba(OH)2 alone (n = 1) in water. In each of the crystal structures of K2(O3S)2CHF and K2(O3S)2CF2, there is an eight-coordinate and a six-coordinate potassium ion, whilst in K2(O3S)2(CF2)3H2O, two different eight-coordinate potassium ions are linked by a bridging water molecule. One potassium has additionally six sulfonate oxygen and one fluorine donor atoms, and the other, five sulfonate oxygens and two fluorine donor atoms. The preparation of highly crystalline [Nien3][(O3S)(CF2)n] (en = ethane-1,2-diamine; n = 1, 3–5) and the X-ray crystal structures for n = 1 or 3 provide evidence for the value of perfluoroalkanedisulfonate ions as counter ions for the crystallization of cationic complexes. Darstellung von Barium-, Kalium- und Tris(ethan-1,2-diamin)nickel(II)perfluoroalkandisulfonaten und Kristallstrukturen von K2(O3S)2CHF, K2(O3S)2CF2, K2(O3S)2(CF2)3 · H2O und [Ni(en)3](O3S)2(CF2)n; (n = 1, 3) Die Umsetzung von (CF2)n(SO2F)2 (n = 1, 3–5) und CHF(SO2F)2 mit CaO, M(OH)x und Wasser (M = K; x = 1; M = Ba; x = 2) ergab die Salze K2((CF2)n(SO3)2), Ba[(CF2)n(SO3)2] und K2[CHF(SO3)2]. Sowohl in der Struktur von K2(O3S)2CHF wie auch von K2(O3S)2CF2 liegt ein 8-fach koordiniertes und ein 6-fach koordiniertes Kalium-Ion vor, wahrend im K2[(O3S)2(CF2)3]H2O zwei verschiedene, jeweils 8-fach koordinierte Kalium-Ionen uber ein verbruckendes Wassermolekul verknupft sind. Ein Kalium-Ion hat zusatzlich 6 Sulfonat-Sauerstoff- und ein Fluor-Donoratom, das andere funf Sulfonat-Sauerstoff- und zwei Fluor-Donoratome. Die Perfluoroalkandisulfonationen erweisen sich als sehr gut geeignete Gegenionen fur die Kristallisation kationischer Komplexe, wie [Ni(en)3][(CF2)n(SO3)2] (en = Ethan-1,2-diamin; n = 1; 3–5, deren Kristallstrukturen fur n = 1, 3 ermittelt wurden.

The X-ray crystal structures of Hg(C6F4X-p)2 (X = NH2, OMe, or Me) show the compounds to have almost linear C–Hg–C stereochemistry (X = NH2, 176.3(4)°; X = OMe, 179.5(2)°; X = Me, 176.3(2)°), and the two tetrafluoroaryl rings rotated ca. 52–62° with respect to each other. Substantial conjugation of NH2 and OMe groups with the aromatic rings is evident from N–C and O–C(Ar) distances. For X = NH2 or OMe, two weak N(O)–Hg coordination interactions per mercury lead to a two dimensional supramolecular chain structure containing pairs of π-stacked aromatic rings at near van der Waals contact distances rotated at 62.2° (X = NH2) or 52.9° (X = OMe) to each other. In Hg(C6F4Me-p)2, which does not have potential donor atoms, no supramolecular structure is obtained, the molecules being laterally displaced from one another. Organoquecksilber-Verbindungen. 33 Die Kristallstrukturen von Hg(C6F4X-p)2 (X = NH2, OMe, Me) – Zwei Beispiele fur supramolekulare Lewis-Saure-Base-Komplexe In den Kristallstrukturen von Hg(C6F4X-p)2 (X = NH2, OMe, or Me) liegen nahezu lineare C–Hg–C-Gruppen vor (X = NH2, 176,3(4)°; X = OMe, 179,5(2)°; X = Me, 176,3(2)°); die beiden Tetrafluoroaryl-Ringe sind um 52–62° gegeneinander verdreht. Aus den Abstanden N–C und O–C(Ar) ergibt sich eine deutliche Konjugation der NH2- und OMe-Gruppen mit den aromatischen Ringen. Zwei schwache koordinative N(O)–Hg-Wechselwirkungen pro Hg-Atom ergeben fur X = NH2 bzw. OMe eine zweidimensionale supramolekulare Kettenstruktur aus Paaren von uber π-Wechselwirkungen gestapelten aromatischen Ringen mit nahezu van der Waals-Kontakten; die aromatischen Ringe sind um 62,2° (X = NH2) bzw. 52,9° (X = OMe) gegeneinander verdreht. Hg(C6F4Me-p)2 hat keine potentiellen Donor-Atome; folgerichtig wird keine supramolekulare Struktur beobachtet, die Molekule liegen seitwarts nebeneinander.

The complexes [K(H2O)2LnL2] (Ln = La or Nd; L = 1,2-benzenedisulfonate) and [K(H2O)Yb(H2O)4L2] were initially isolated fortuitously from attempts to prepare the corresponding Ln2L3 complexes from Ln2O3 and H2L in water. Indeed the bulk products from these reactions have the composition Ln2L3. Subsequently, deliberate syntheses by reacting equimolar amounts of Ln2L3 with K2L in water gave the complexes in good yield. X-ray crystal structures of [K(H2O)2LnL2] (Ln = La or Nd) showed the complexes to be isostructural with a two dimensional polymeric network structure in which LnL2 units are linked into chains crosslinked by potassium ions. Each Ln is nine coordinate with solely sulfonate oxygen donor atoms. Between adjacent lanthanoid ions there are three different types of sulfonate bridges and two examples of each. Most noteworthy is highly unsymmetrical bridging through μ-η2-sulfonate oxygen atoms. Consequently, one Ln–O bond is ca. 0.5 A longer than the other eight. Potassium is nine-coordinate with seven sulfonate oxygen atoms and two aqua ligands, and surprisingly is much longer than . Pairs of potassium ions are linked by two μ-η2-sulfonate oxygen atoms, which are unsymmetrically bridging. The structure of [K(H2O)Yb(H2O)4L2] comprises discrete tetranuclear units containing two independent ytterbium ions, each coordinated by four water molecules and two chelating (via seven membered rings) disulfonate ligands, and two potassium ions, each coordinated by six sulfonate oxygen atoms and a water molecule. For each potassium, four of the coordinated sulfonate oxygen atoms are from sulfonate ligands bonded to one ytterbium atom and two from sulfonate ligands attached to the other ytterbium atom. In contrast to the Nd and La complexes, is shorter than . Synthese und Kristallstrukturen von Kalium–Lanthanoid(III) Komplexen mit 1,2-Benzoldisulfonat als Liganden Bei Versuchen zur Synthese der Verbindungen Ln2L3 aus Ln2O3 und H2L (Ln = La, Nd, Yb; L = 1,2-Benzoldisulfonat) in Wasser wurden auch die Komplexe [K(H2O)2LnL2] (Ln = La, Nd) und [K(H2O)Yb(H2O)4L2] erhalten. Die analytische Zusammensetzung der Produkte entspricht tatsachlich Ln2L3; die neuen Komplexe wurden daraufhin aus Ln2L3 und K2L in guter Ausbeute gewonnen. Nach Ausweis von Einkristallstrukturanalysen sind die Komplexe [K(H2O)2LnL2] (Ln = La, Nd) isotyp, sie bilden ein zweidimensionales polymeres Netzwerk, in dem LnL2-Einheiten zu Ketten angeordnet sind, die durch Kaliumatome miteinander verknupft sind. Die Zentralteilchen Ln3+ sind neunfach von einzelnen Sulfonat-Sauerstoffatomen koordiniert. Zwischen benachbarten Lanthanoidionen gibt es drei verschiedene Typen von Sulfonatbrucken. Bemerkenswert ist die sehr unsymmetrische Brucke zwischen μ-η2-Sulfonat-Sauerstoffatomen. Folglich ist eine Ln–O-Bindung ca. 0.5 A langer als die anderen acht. Kalium ist neunfach von sieben Sulfonat-Sauerstoffatomen und zwei Wassermolekulen koordiniert, uberraschenderweise ist viel langer als . Die Kaliumionen sind paarweise uber zwei unsymmetrisch verbruckende μ-η2-Sulfonat-Sauerstoffatome miteinander vernetzt. Die Kristallstruktur von [K(H2O)Yb(H2O)2L2] besteht aus vierkernigen Einheiten, die zwei Kalium- und zwei voneinander unabhangige Ytterbiumatome enthalten, von denen jedes von vier Wassermolekulen und zwei chelatisierenden Disulfonatliganden koordiniert ist. Die beiden Kaliumatome sind von sechs Sulfonat-Sauerstoffatomen und einem Wassermolekul umgeben. Vier der an Kalium koordinierten Sauerstoffatome gehoren Sulfonatliganden an, die an ein Ytterbiumatom gebunden sind, zwei gehoren zu Sulfonatliganden, die an das andere Ytterbiumatom gebunden sind. Im Gegensatz zu den Nd- und La-Komplexen ist hier kurzer als .

Structures of the new complexes [La(Odpp)3(dig)]·0.5dig (Odpp = 2,6-diphenylphenolate; dig = bis(2-methoxyethyl) ether – diglyme) and [Nd(Odpp)3(py)2]·2py (py = pyridine), obtained by crystallization of the corresponding [Ln(Odpp)3(thf)2] complex from diglyme or pyridine contain six-coordinate and five-coordinate lanthanoid atoms respectively. In the former, two meridional sets of donor atoms, (O3(dig) and O3(Odpp)) are near normal to each other and in a highly distorted octahedral stereochemistry, whereas the latter is trigonal bipyramidal with an oxygen and a nitrogen atom apical and a pronounced lengthening of the axial Nd-N bond.

Reaction of 8-hydroxyquinoline (HOQ) with calcium and neodymium metal (mole ratio 1.6:0.72:1.1) in the presence of mercury at 110 °C under vacuum in a durene flux yielded bis(8-quinoli-nolato-κ:N, O(Nd))hexakis(μ-(O)-8-quinolinolato-κ:N(Nd), O(Nd, Ca))calcium(II) dineodymium(III) (NdCaNd) (1) (, a = 11.305(2), b = 12.468(3), c = 13.918(3) A, α = 116.62(3), β = 95.46(3), γ = 109.59(3)°, V = 1580.6(6) A3, R1 = 0.0718). The trimetallic was again obtained but as the solvate 1. (HOQ) from reaction between HOQ, Nd and Ca, (mole ratio 2.8:2:1) in a 1, 3, 5-tri-tert-butylbenzene flux , a = 10.206(2), b = 12.256(3), c = 13.819(3) A, α = 85.93(3), β = 89.94(3), γ = 81.36(3)°, V = 1704.5(6) A3, R1 = 0.0592).

A central μ3—O moiety linking two FeIII and one CeIII sites supported by two distinct heterometallic carboxylate bridging modes features in self-assembled [CeFe2(bpy)2(μ3—O)(μ—L)2(μ—LH)2(LH)(H2O)2]·0.5(bpy)·7H2O (1) (LH2 = glycolic acid), and the structure models potential bonding modes of the Rare Earth corrosion inhibitor Ce(glycolate)3 to iron or iron oxide.

Transparent orange crystals of [Yb(MeCp)2(O2CC6F5)]2 and [Yb(MeCp)2(O2C-o-HC6F4)]2 were obtained by oxidation of Yb(MeCp)2 with M(O2CR) (M = 1/2 Hg, Tl; R = C6F5, o-HC6F4) in tetrahydrofuran. They have a dimeric structure with bridging bidentate (O, O')-benzoate groups and eight coordinated ytterbium. Both crystallise isotypic in the orthorhombic space group Pbca. Room temperature as well as low temperature single crystal X-ray investigations show the o-H/F positions in [Yb(MeCp)2(O2C-o-HC6F4)]2 not to be ordered.

From the reaction of PtCl2(hex) (hex = hexa-1,5-diene) with LiC6F5 in diethyl ether, the complex [Pt{CH(CH2C6F5)CH2CH2CH=CH2}(C6F5)(OH2)] (1) was isolated. The crystal structure (monoclinic, C2/c (no. 15), Z = 8, a = 15.241(3), b = 16.579(2), c = 16.225(2) A, β = 111.12(2)°) shows a complex with square planar coordination around platinum with a template formed 1-pentafluorophenylhex-5-en-2-yl ligand, and C6F5 and aqua ligands trans to the double bond and alkyl carbon, respectively.

The title compound [YbCl3(py)4]·0.5py has been grown as single crystals by the treatment of ytterbium chunks with hexachloroethane in pyridine and characterized by a single crystal X-ray study. It is isomorphous with the previous [LnCl3(py)4]·0.5py array defined for Ln = La, Eu, Er, extending the ‘domain of existence’ of that form to Ln = Yb, an unexpected result given that the Ln = Y adduct with similar seven-coordinate, pentagonal bipyramidal coordination environment, is of an unsolvated form.

Transparent orange-red crystals of [Yb(MeCp)2(O2CPh)]2 obtained by oxidation of Yb(MeCp)2 with Tl(O2CPh) in tetrahydrofuran have a dimeric structure with bridging bidentate (O,O′)-benzoate groups and eight-coordinate ytterbium.