Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von trans-(PNP)[TcCl4(Py)2] und trans-(PNP)[TcBr4(Py)2]

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of trans-(PNP)[TcCl₄(Py)₂] and trans-(PNP)[TcBr₄(Py)₂] By reaction of (PNP)₂[TcX₆] with pyridine in the presence of [BH₄]^? (PNP)[TcX₄(Py)₂], X = Cl, Br, are formed. X-ray structure determinations on single crystals of these isotypic Tc^III complexes (monoclinic, space group P2₁/n, Z = 2, for X = Cl: a = 13.676(4), b = 9.102(3), c = 17.144(2) Å, β = 91.159(1)°; for X = Br: a = 13.972(2), b = 9.146(3), c = 17.285(4) Å, β = 90.789(2)°) result in the averaged bond distances Tc? Cl: 2.386, Tc? Br: 2.519, Tc? N: 2.132(3) (X = Cl) and 2.143(4) Å (X = Br). The two pyridine rings are coplanar and vertical to the X? Tc? X-axes, forming angles of 42.28° (X = Cl) and 43.11° (X = Br). Using the molecular parameters of the X-ray structure determination and assuming D_2h point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis based on a modified valence force field. Good agreement between observed and calculated frequencies is obtained with the valence force constants f_d(TcCl) = 1.45, f_d(TcBr) = 1.035, f_d(TcN) = 1.37 (X = Cl) and 1.45 mdyn/ Å (X = Br), respectively.     

Dimolybdenum Complexes Containing Pairs of Bridging Diphosphine and Carboxylate Ligands. Synthesis and Structures of trans-Mo2(O2CCH3)2(μ-dppa)2(BF4)2 and trans-Mo2X2(O2C(CH2)nCH3)2(μ-dppa)2 (n = 2, 10 or 12; X = Cl or Br; dppa = N,N-Bis(diphenylphosphino)amine)

The red complex trans-Mo₂(O₂CCH₃)₂(μ-dppa)₂(BF₄)₂, 1 , was prepared by reaction of [Mo₂(O₂CCH₃)₂(CH₃CN)₆][BF₄]₂ with dppa (dppa = Ph₂PN(H)PPh₂) in THF. The reactions of Mo₂(O₂C(CH₂)_nCH₃)₄ with dppa and (CH₃)₃SiX (X = Cl or Br) afforded the complexes trans-Mo₂X₂(O₂C(CH₂)_nCH₃)₂(μ-dppa)₂ (X = Cl, n = 2, 2; X = Br, n = 2, 3; X = Cl, n = 10, 4 ; X = Cl, n = 12, 5 ). Their UV-vis, IR and ³¹P{¹H}-NMR spectra have been recorded and the structures of 1, 2 and 3 have been determined. Crystal data for 1 : space group P2₁/n, a = 12.243(1) Å, b = 17.222(1) Å, c = 13.266(1) Å, β = 95.529(1)°, V = 2784.1(6) ų, Z = 2, with final residuals R = 0.0509 and Rw = 0.0582. Crystal data for 24CH₃Cl₂: space group P2₁/n, a = 13.438(1) Å, b = 19.276(1) Å, c = 14.182(1) Å, β = 111.464(1)°, V = 3418.9(6) ų, Z = 2, with final residuals R = 0.0492 and Rw = 0.0695. Crystal data for 3·4CH₂Cl₂: space group P2₁/n, a= 13.579(1) Å, b = 19.425(1) Å, c = 14.199(1) Å, β = 111.881(2)°, V = 3475.6(7) ų, Z = 2, with final residuals R = 0.0703 and Rw = 0.0851. Comparison of the structural data shows that the effect of the axial ligand on weakening the Mo-Mo bond strength is X^? > CH₃CN > BF₄^?. The T_m values are 121.7 °C for 2 , 111.1 °C for 3 and 91.5 °C for 5 , respectively.     

Darstellung,Kristallstrukturen und Eigenschaften der Chrom(II)-phosphat-halogenide Cr2(PO4)Br und Cr2(PO4)I

Synthesis, Crystal Structures, and Properties of the Chromium(II) Phosphate Halides Cr₂(PO₄)Br and Cr₂(PO₄)I The new compounds Cr₂(PO₄)Br and Cr₂(PO₄)I have been obtained by reaction of CrPO₄, Cr and Br₂ or I₂ in evacuated silica tubes at elevated temperatures (Cr₂(PO₄)Br: 900 °C, Cr₂(PO₄)I: 700 °C). Single crystals of deep blue Cr₂(PO₄)Br and turquoise Cr₂(PO₄)I with edge-lengths up to 2 mm and 0.3 mm, respectively, have been grown in experiments involving the gaseous phase. Single crystal data have been used for structure determination and refinement. Though being not isotypic, the two crystal structures are closely related. Two crystallographically independent Cr²⁺, in polyhedra [Cr1O₃X₃] and [Cr2O₅X], form dimers [Cr1₂O₂O_2/2X₄] and [Cr2₂O₈X₂]. Distances are 1.978 Å ≤ d(Cr–O) ≤ 2.096 Å (for the iodide: 1.959 Å ≤ d(Cr–O) ≤ 2.105 Å), 2.587 Å ≤ d(Cr–Br) ≤ 3.158 Å and 2.867 Å ≤ d(Cr–I) ≤ 3.327 Å. The structures of bromide and iodide can be distinguished by the different way of connection of the Cr1 containing dimers. The phosphate group shows slightly distorted tetrahedral geometry with 1.491 Å ≤ d(P–O) ≤ 1.559 Å (1.486 Å ≤ d(P–O) ≤ 1.567 Å) and angles of 106.48° ≤ ∠(O–P–O) ≤ 111.69° (106.57° ≤ ∠(O–P–O) ≤ 111.72°. IR-spectra of Cr₂(PO₄)Br and Cr₂(PO₄)I, the Raman-spectrum of Cr₂(PO₄)Br and electronic spectra of the two compounds in the UV/vis region at low temperature are reported and discussed.     

Tetra(3‐methoxypropionato)diruthenium(II,III) Units: Supramolecular Organization in the Complex [Ru2(μ‐O2CCH2CH2OMe)4(H2O)2]BF4

The synthesis and characterization of Ru₂Cl(μ‐O₂CCH₂CH₂OMe)₄ ( 1 ), [Ru₂(μ‐O₂CCH₂CH₂OMe)₄(H₂O)₂]BF₄ ( 2 ), PPh₄[Ru₂Cl₂(μ‐O₂CCH₂CH₂OMe)₄] ( 3 ), (PPh₄)₂[Ru₂Br₂(μ‐O₂CCH₂CH₂OMe)₄]NO₃ ( 4 ), and (PPh₄)₂[Ru₂I₂(μ‐O₂CCH₂CH₂OMe)₄]I_0.5(NO₃)_0.5 ( 5 ), are described. The structure of complexes 2 – 5 was established by single crystal X‐ray diffraction. All complexes show a diruthenium(II, III) unit bridged by four 3‐methoxypropionate ligands. The cationic complex 2 have two axially coordinated water molecules, with a Ru–Ru bond distance of 2.2681(12) Å. This complex shows a supramolecular two‐dimensional organization across hydrogen bonded between the axial water molecules and two methoxy groups of adjacent diruthenium units. The metal‐metal bond lengths, in the anionic complexes 3 , 4 , and 5 , are 2.3039(5), 2.3077(6), and 2.3115(8) Å, respectively. These distances are longer than the observed in compound 2 . In the anionic complexes, the axial positions of the diruthenium units are occupied by two halide ligands. Complexes 3 – 5 have PPh₄⁺ cations as counterion, although 4 and 5 are double salts with PPh₄NO₃ and PPh₄I_0.5(NO₃)_0.5, respectively. All compounds have been also characterized by elemental analysis, magnetic measurements, and spectroscopic techniques.     

Nitrosyltechnetium(I) Complexes with 2‐(Diphenylphosphanyl)aniline

[Tc^I(NO)Cl(H₂L1)₂]⁺ cations (H₂L1 = 2‐(diphenylphosphanyl)aniline) are formed during reactions of H₂L1 with (NBu₄)[Tc(NO)Cl₄(MeOH)] or (NH₄)TcO₄/HCl/NH₂OH mixtures. Different isomers were isolated depending on the counterions and solvents used. The technetium(I) complexes cis‐NO,Cl,trans‐P,P‐[Tc^I(NO)Cl(H₂L1)₂]Cl, trans‐NO,Cl,cis‐P,P‐[Tc^I(NO)Cl(H₂L1)₂]₂(TcCl₆), and trans‐NO,Cl,trans‐P,P‐[Tc^I(NO)Cl(H₂L1)₂](PF₆) were isolated in crystalline form and studied by spectroscopic methods and X‐ray crystallography. DFT calculations show that there are only minor energy differences between the three isomers and the formation of the individual compounds is most probably strongly influenced by interactions with solvents and counterions.     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.     

Magnesiumphthalocyanine: Darstellung und Eigenschaften von Halogenophthalocyaninatomagnesat, [Mg(X)Pc2−]− (X = F,Cl, Br); Kristallstruktur von Bis(triphenylphosphin)iminiumchloro(phthalocyaninato)magnesat-Aceton-Solvat

Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc^2?]^? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((ⁿBu₄N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc^2?]^?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (ⁿBu₄N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of ^b(PNP)[Mg(Cl)Pc^2?] · CH₃COCH₃ reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (N_iso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? N_iso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (^b(PNP)⁺: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed.     

Synthese und Eigenschaften von cis-Diacidophthalocyaninato(2–)thallaten(III); Kristallstruktur von Tetra(n-butyl)ammonium-cisdinitrito(O,O′)- und -cis-dichlorophthalocyaninato(2–)thallat(III)

Syntheses and Properties of cis -Diacidophthalocyaninato(2–)thallates(III); Crystal Structure of Tetra(n-butyl)ammonium cis -dinitrito(O,O ′)- and cis -dichlorophthalocyaninato(2–)thallate(III) Blue green cis-diacidophthalocyaninato(2–)thallate(III), ^cis[Tl(X)₂pc^2–]^– (X = Cl, ONO′, NCO) is prepared from iodophthalocyaninato(2–)thallium(III) and the corresponding tetra(n-butyl)ammonium salt, (ⁿBu₄N)X in dichloromethane, and isolated as (ⁿBu₄N)^cis[Tl(X)₂pc^2–]. (ⁿBu₄N)^cis[Tl(ONO′)₂pc^2–] ( 1 ) and (ⁿBu₄N)^cis[Tl(X)₂pc^2–] · 0,5 (C₂H₅)₂O ( 2 ) crystallize in the monoclinic space group P2₁/n with cell parameters for 1: a = 14.496(2) Å, b = 17.293(5) Å, c = 18.293(2) Å, β = 98.76(1)° resp. for 2 : a = 13.146(1) Å, b = 14.204(5) Å, c = 24.900(3) Å, β = 93.88(1)°; Z = 4. In 1 , the octa-coordinated Tl atom is surrounded by four isoindole-N atoms (N_iso) and four O atoms of the bidental nitrito(O,O′) ligands in a distorted antiprism. The Tl–N_iso distances vary between 2.257(3) and 2.312(3) Å, the Tl–O distances between 2.408(3) and 2.562(3) Å. In 2 , the hexa-coordinated Tl atom ligates four N_iso atoms and two Cl atoms in a typical cis-arrangement. The average Tl–N_iso distance is 2.276 Å, the average Tl–Cl distance is 2.550 Å. In 1 and 2 , the Tl atom is directed out of the centre of the (N_iso)₄ plane (Ct_N) towards the acido ligands (d(Tl–Ct_N) = 1.144(1) Å in 1 , 1.116(2) Å in 2 ), and the phthalocyaninato ligand is concavely distorted. The vertical displacements of the periphereal C atoms amounts up to 0.82 Å. The optical and vibrational spectra as well as the electrochemical properties are discussed.     

Präparation,Kristallstruktur und thermisches Verhalten der Quecksilber(I)phosphate α-(Hg2)3(PO4)2, β-(Hg2)3(PO4)2 und (Hg2)2P2O7

Contributions on Crystal Structures and Thermal Behaviour of Anhydrous Phosphates. XXIII. Preparation, Crystal Structure, and Thermal Behaviour of the Mercury(I) Phosphates α-(Hg₂)₃(PO₄)₂, β-(Hg₂)₃(PO₄)₂, and (Hg₂)₂P₂O₇ Light-yellow single crystals of (Hg₂)₂P₂O₇ have been obtained via chemical vapour transport in a temperature gradient (500 °C → 450 °C, 23 d) using Hg₂Cl₂ as transport agent. Characteristic feature of the crystal structure (P2/n, Z = 2, a = 9,186(1), b = 4,902(1), c = 9,484(1) Å, β = 98,82(2)°, 1228 independent of 5004 reflections, R(F) = 0,066 for 61 variables, 7 atoms in the asymmetric unit) are Hg₂²⁺-units with d(Hg1–Hg1) = 2,508 Å and d(Hg2–Hg2) = 2,519 Å. The dumbbells Hg₂²⁺ are coordinated by oxygen, thus forming polyhedra [(Hg1₂)O₄] and [(Hg2₂)O₆]. These polyhedra share some oxygen atoms. In addition they are linked by the diphosphate anion P₂O₇^4– (ecliptic conformation; ∠(P,O,P) = 129°) to built up the 3-dimensional structure. Under hydrothermal conditions (T = 400 °C) orange single crystals of the mercury(I) orthophosphates α-(Hg₂)₃(PO₄)₂ and β-(Hg₂)₃(PO₄)₂ have been obtained from (Hg₂)₂P₂O₇ and H₃PO₄ (c = 1%). The crystal structures of both modifications have been refined from X-ray single crystal data [α-form (β-form): P2₁/c (P2₁/n), Z = 2 (2), a = 8,576(3) (7,869(3)), b = 4,956(1) (8,059(3)), c = 15,436(3) (9,217(4)) Å, β = 128,16(3) (108,76(4))°, 1218 (1602) independent reflections of 4339 (6358) reflections, R(F) = 0,039 (0,048) for 74 (74) variables, 8 (8) atoms in the asymmetric unit]. In the structure of α-(Hg₂)₃(PO₄)₂ three crystallographically independent mercury atoms, located in two independent dumbbells, are coordinated by three oxygen atoms each. Thus, [(Hg₂)O₆] dimers with a strongly distorted tetrahedral coordination of all mercury atoms are formed. Such dimers are present besides [(Hg₂)O₅]-polyhedra in the less dense crystal structure of β-(Hg₂)₃(PO₄)₂ (d(Hg–Hg) = 2,518 Å). The mercury(I) phosphates are thermally labile and disproportionate between 200 °C (β-(Hg₂)₃(PO₄)₂) and 480 °C (α-(Hg₂)₃(PO₄)₂) to elemental mercury and the corresponding mercury(II) phosphate.     

Unusual Structural Features in the Lysozyme Derivative of the Tetrakis(acetato)chloridodiruthenium(II,III) Complex

The reaction between the paddle‐wheel tetrakis(acetato)chloridodiruthenium(II,III) complex, [Ru₂(μ‐O₂CCH₃)₄Cl] and hen egg‐white lysozyme (HEWL) was investigated through ESI‐MS and UV/Vis spectroscopy and the formation of a stable metal–protein adduct was unambiguously demonstrated. Remarkably, the diruthenium core is conserved in the adduct while two of the four acetate ligands are released. The crystal structure of this diruthenium–protein derivative was subsequently solved through X‐ray diffraction analysis to 2.1 Å resolution. The structural data are in agreement with the solution results. It was found that HEWL binds two diruthenium moieties, at Asp101 and Asp119, respectively, with the concomitant release of two acetate ligands from each diruthenium center.     

Preparation,characterization, crystal and molecular structure of Na2[N(CH2COO)3 99Tc(IV) (μ-O)2 99Tc(IV)N(CH2COO)3] · 6H2O

The title compound and its potassium analog have been prepared from corresponding aqueous solutions of ⁹⁹TcO at pH ≈? 2 with SO₂ as a reducing agent. An X-ray structure determination of the Na-salt showed Tc coordinated to the tetradentate N(CH₂COO) ligand (NTA). Two Tc-NTA moieties are joined via two bridging O-atoms into a four-membered Tc₂O₂ ring. The observed diamagnetism, a strong absorption band at 19 950 cm^?1, and a short Tc-Tc distance of 2.363 Å are typical for the Tc₂O₂-fragment with its strong metal-metal interaction. The structural trans-influence at Tc and the network of H-bonds are consistent with Tc in oxidation state IV.     

Synthesis and Crystal Structure of Two New Molydenum(V) Pyrophosphate Complexes

Two new reduced molybdenum pyrophosphates, Na₂₈[Na₂{(Mo₂O₄)₁₀(P₂O₇)₁₀(HCOO)₁₀}]·108H₂O ( 1 ) and Na₂₂(H₃O)₂[Na₄{(Mo₂O₄)₁₀(P₂O₇)₁₀(CH₃COO)₈(H₂O)₄}]·91H₂O ( 2 ) have been synthesized and characterized by single‐crystal X‐ray diffraction. Red crystals of 1 are triclinic, space group , with a = 17.946(4) Å, b = 18.118(4) Å, c = 21.579(4) Å, α = 114.47(3)°, β = 93.54(3)°, γ = 114.39(3)° and V = 5581.8(19) ų, and orange crystals of 2 are monoclinic, space group P2₁/n, with a = 21.467(4) Å, b = 23.146(5) Å, c = 24.069(5) Å, β = 101.76(3)° and V = 11708(4) ų. They are both constructed by Mo^V dimers ({Mo₂O₄(O_P)₄(HCOO)} in 1 , {Mo₂O₄(O_P)₄(CH₃COO)} and {Mo₂O₄(O_P)₄(H₂O)₂} in 2 ) and pyrophosphoric groups. Their structures can be described as two interconnected nonequivalent wheels which are approximately perpendicular, delimiting a large cavity. The larger wheel contains six Mo^V dimers, while the smaller one has four dimers.     

Review of technetium chemistry research conducted at the University of Nevada Las Vegas

The chemistry of technetium is being explored at the University of Nevada Las Vegas. Our goal is to investigate both the applied and fundamental aspects of technetium chemistry, with a special emphasis on synthesis, separations, and materials science. The synthetic chemistry focuses on metal–metal multiple bonding, oxides and halides. Synthesis and characterizations of (n-Bu₄N)₂Tc₂X₈, Tc₂(O₂CCH3)₄X₂ (X = Cl, Br), TcO₂, Bi₂Tc₂O₇, Bi₃TcO₈, TcBr₃ and TcBr₄ have been performed. The applied chemistry is related to the behavior of Tc in the UREX process. Separation of U/Tc has been conducted using anion exchange resin and metallic Tc waste form synthesized and characterized.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Darstellung der Halogeno-Pyridin-Rhenate(III), [ReX6−n (Py)n](3−n)− (X = Br,Cl; n = 1−3), sowie Kristallstrukturen von trans-[(C4H9)4N][ReBr4(Py)2], mer-[ReCl3(Py)3] und mer-[ReBr3(Py)3]

Preparation of Halogeno Pyridine Rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl; n = 1?3) Crystal Structures of trans-[(C₄H₉)₄N][ReBr₄(Py)₂], mer-[ReCl₃(Py)₃], and mer- [ReBr₃(Py)₃] The mixed halogeno-pyridine-rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl), n = 1?3, have been prepared for the first time by reaction of the tetrabutylammoniumsalts (TBA)₂[ReX₆] (X = Br, Cl) in pyridine with (TBA)BH₄ and separation by chromatography on Al₂O₃. Apart from the monopyridine complexes only the trans and mer isomers are formed from the bis-and tris-pyridine compounds. The X-ray structure determinations of the isotypic neutral complexes mer- [ReX₃(Py)₃] (monoclinic, space group P 2₁/n, Z = 4; for X = Cl: a = 9,1120(8), b = 12,5156(14), c = 15,6100(13) Å, β = 91,385(7)°; for X = Br: a = 9,152(5), b = 12,852(13), c = 15,669(2) Å, β = 90,43(2)°) reveal, due to the stronger trans influence of pyridine compared with Cl and Br, that the Re? X distances in asymmetric Py? Re? X3 axes with ReCl3 = 2,397 Å and ReBr3 = 2,534 Å are elongated by 1,3 and 1% in comparison with symmetric X1? Re? X2 axes with ReCl1 = ReCl2 = 2,367 Å and ReBr1 = 2,513 and ReBr2 = 2,506 Å, respectively. The Re? N bond lengths are roughly equal with 2,12 Å. Trans-(TBA)[ReBr₄(Py)₂] crystallizes triclinic, space group P1 , a = 9,2048(12), b = 12,0792(11), c = 15,525(2) Å, α = 95,239(10), β = 94,193(11), γ = 106,153(9)°, Z = 2. The unit cell contains two independent but very similar complex anions with approximate D_2h(mmm) point symmetry.     

Technetium Complexes with 2‐Mercapto‐methyltetrazolate

2‐Mercapto‐methyltetrazolate, Smetetraz^–, acts as monoanionic, monodentate ligand in a number of technetium compounds. Anionic Tc^V complexes of the types [TcO(Smetetraz)₄]^– and [TcN(Smetetraz)₄]^2– are formed when (Bu₄N)[Tc^VOCl₄] or (Bu₄N)[Tc^VINCl₄], respectively, react with Na(Smetetraz). Reduction of the metal takes place in the latter case. (Bu₄N)₂[TcN(Smetetraz)₄] crystallises in the monoclinic space group Pc (a = 9.701(5), b = 17.570(5), c = 16.821(10) Å, β = 96.50(3)°, Z = 2). The Tc atom is situated 0.580(3) Å above the basal plane of a square pyramid which is formed by the sulfur atoms and the nitrido ligand as its apex. The Tc–S bond lengths lie between 2.384(3) and 2.410(3) Å. [Tc(PPh₃)(Smetetraz)₃(CH₃CN)] is formed during the reaction of [TcCl₃(PPh₃)₂(CH₃CN)] with NaSmetetraz as blue needles with co‐crystallised solvent toluene (space group C2/c, a = 24.188(4), b = 14.373(1), c = 25.617(5) Å, β = 109.48(1)°, Z = 8). The metal atom is coordinated by PPh₃ and CH₃CN in the axial position of a trigonal bipyramid. All three aryl rings are on the sterically less strained side of the plane defined by the sulfur atoms. The Tc–S bond lengths range between 2.233(2) and 2.247(2) Å.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von (n‐Bu4N)2[PtX4(ox)], X = Cl,BR

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (n‐Bu₄N)₂[PtX₄(ox)], X = Cl, Br By oxidation of (n‐Bu₄N)₂[PtX₂(ox)], X = Cl, Br, with Cl₂ or Br₂ in dichloromethane (n‐Bu₄N)₂[PtCl₄(ox)] ( 1 ) and (n‐Bu₄N)₂[PtBr₄(ox)] ( 2 ) are formed. The crystal structure of [(C₅H₅N)₂CH₂][PtCl₄(ox)] (monoclinic, space group C2/m, a = 15.562(1), b = 13.779(1), c = 10.168(1)Å, ß = 128.099(9)°, Z = 4) reveals complex anions with nearly C_2v point symmetry. The bond lengths in the Cl′‐Pt‐O^˙ axes are Pt‐Cl′ = 2.287 and Pt‐O^˙ = 2.048 and in the Cl‐Pt‐Cl axis Pt‐Cl = 2.314Å. The oxalato ligand is nearly plane with an O‐C‐C‐O torsion angle of 0.5°. In the vibrational spectra the PtX stretching vibrations are observed at 328 and 353 ( 1 ) and 201 and 212 cm^—1 ( 2 ). The PtX′ modes appear at 360 and 343 ( 1 ) and 227 and 238 cm^—1 ( 2 ). The PtO^˙ stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 400—800 cm^—1. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl) = 2.08, f_d(PtCl′) = 2.29, f_d(PtBr) = 1.56, f_d(PtBr′) = 2.02 and f_d(PtO^˙) = 2.46 ( 1 ) and 2.35 mdyn/Å ( 2 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 5623.0 ( 1 ) and 4536.1 ( 2 ).     

Technetium(VII)-oxid: Ein Übergangsmetalloxid mit Molekülstruktur im festen Zustand

Tc₂O₇ crystallizes in the orthorhombic space group Pbca with a = 13.756, b = 7.439, c = 5.617 Å, Z = 4. The single crystal structure analysis shows the crystals to contain isolated centrosymmetric Tc₂O₇ molecules with a linear central Tc? O? Tc bridge and with, tetrahedral coordination of the Tc atoms. Tc? O bond lengths: 1.840 (bridge), 1.658, 1.684 and 1.706 Å. The structure is more closely related to CrO₃, RuO₄ and OsO₄ than to Re₂O₇. Structural properties of the d° transition metal oxides are briefly discussed.     

Synthese und Eigenschaften von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(halogenophthalocyaninato(2–)ferraten(IV)); Kristallstruktur von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(fluorophthalocyaninato(2–)ferrat(IV))-Trihydrat

Synthesis and Properties of Bis(tetra(n-butyl)ammonium)μ-Carbido-di(halophthalocyaninato(2–)ferrates(IV)); Crystal Structure of Bis(tetra(n-butyl)ammonium) μ-Carbido-di(fluorophthalocyaninato(2–)ferrate(IV)) Trihydrate μ-Carbido-di(pyridinephthalocyaninato(2–)iron(IV)) reacts with tetra(n-butyl)ammonium halide (ⁿBu₄N)X) in solution (X = F) or in a melt (X = Cl, Br) to yield bis(tetra(n-butyl)ammonium μ-carbido-di(halophthalo-cyaninato(2–)ferrat(IV)). The fluoro-complex salt crystallizes as a trihydrate monoclinically in the space group P12₁/n1 with the following cell parameters: a = 15.814(1) Å; b = 22.690(5) Å; c = 25.127(3) Å; β = 98.27(1)°, Z = 4. The Fe atoms are almost in the centre (Ct) of the (N_iso)₄ planes (N_iso: isoindoline-N atom) with a Fe–Ct distance of 0.053(1) Å. The average Fe–N_iso distance is 1.939(4) Å, the Fe–(μ-C) distance 1.687(4) Å and the Fe–F distance 2.033(2) Å. The Fe–(μ-C)–Fe core is linear (179.5(3)°). The pc²-ligands are staggered (φ = 42(1)°) with a convex distortion. The asymmetric Fe–(μ-C)–Fe stretch (in cm^–1) is observed in the IR spectra at 917 (X = F), 918 (Cl) and 920 (Br) and the symmetric Fe–(μ-C)–Fe stretch at 476 cm^–1 in the resonance Raman spectra. The IR active asymmetric Fe–X stretch (in cm^–1) absorbs at 336 (X = F), 203 (Cl), 182 (Br), respectively.