Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

Neue ein- und mehrkernige Komplexe der Lanthanoiden. Zur Reaktion von Ph2Se2 mit Ytterbium

New Mono- and Polynuclear Complexes of the Lanthanides. On the Reaction of Ph₂Se₂ with Ytterbium Surprising formation of different complexes during the reaction of Ytterbium with Dichalcogenides. With THF is the mononuclear complex [Yb(SePh)₃(thf)₃] 1 (space group P31c (No. 159), Z = 2, a = 15.353(3) Å, c = 7.8920(10) Å) built up. In this compound is the Lanthanidion octahedrally souronded by the ligands. Reaction in Toluol/THF leads in contrast to the tetranuclear complex [Yb₄(SePh)₈O₂(thf)₆] 2 (space group C2/c (No. 14), Z = 4, a = 27.084(9) Å, b = 13.021(4) Å, c = 24.002(8) Å, β = 106.13(3)°). In DME it is possible to isolate the ionic species [Yb₃(SePh)₆(dme)₄][Yb(SePh)₄(dme)] 3 (space group P1 (No. 2), Z = 2, a = 11.109(3) Å, b = 11.664(2) Å, c = 36.303(10) Å, α = 84.60(4)°, β = 89.52(3)°, γ = 73.69(2)°). In this reactions are neutral and also ionic complexes accesible.     

Die Kristallstruktur von Lithiummesitolat [{LiOC6H2-2,4,6-(CH3)3}4(THF)3]

X-Ray Structure of [{LiOC₆H₂-2,4,6-(CH₃)₃}₄(THF)₃] The title compound crystallized from a THF/OEt₂ solution. Its crystal structure (monoclinic, P2₁/c, a = 21.362(3), b = 13.441(2), c = 17.188(2) Å, β = 98.39(1)°, Z = 4, R = 0,0911, wR² = 0,2562) is built up by cuban-like tetrameric units. Three of the four Li cations attain a coordination number of four by binding to an additional THF molecule. Li(4) without THF coordination has a short distance to one ortho-methyl group (Li(4)…C(27) 2.669(10) Å). The Li–O_ph bonding distances vary from 1.869(10) to 2.051(10) Å (average 1.97 Å); the average bonding distance for Li–O_THF is 2.012(10) Å. Averaged bonding angles for Li–O_ph–Li′ and O_ph–Li–O′_ph amount to 84.4(4)° and 95.4(4)°, respectively. The Li…Li distances significantly differ from each other. They range from 2.556(12) to 2.739(11) Å (average 2.65(1) Å).     

Molecular and Crystal Structures of Cp2YbX(THF) (X = Cl,Br)

Cp₂YbCl(THF) crystallizes in the orthorhombic space group Pnma (Z = 4, a = 13.109(5), b = 11.851(4), c = 9.377(3) Å, R1 = 0.0412, wR2 = 0.0482), while Cp₂YbBr(THF) is monoclinic (P2₁/n, Z = 4, a = 8.149(2), b = 12.997(2), c = 14.388(3) Å, β = 105.73(2)°, R1 = 0.0425, wR2 = 0.0436). The ligand arrangements around the formally eight coordinate Yb atoms are pseudo tetrahedral. These two determinations complete the first series of [Cp₂LnX(L)] (X = F, Cl, Br, I) structures covering all halogens for one lanthanoid and cyclopentadienyl group.     

Synthese und Struktur eines Molybdän–Gadolinium-Heterometall-Komplexes Die Struktur von [Li(thf)4]2[Cp2MoSGdBr4(thf)]2

Synthesis and structure of a Molybdenum–Gadolinium Heterometallic Complex. The Structure of [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂ [Cp₂MoHLi] reacts in THF with S and GdBr₃ to yield the tetranuclear heterobimetallic complex [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂. The bonding situation and the structure of this compound were characterized by X-ray structure analysis (space group P1 (No. 2), Z = 1, a = 10.845(2) Å, b = 12.166(2) Å, c = 15.881(2) Å, α = 101.74(2)°, β = 97.62(2)°, γ = 103.97(2)°). Each S atom of the central Mo₂S₂-ring is coordinated by a GdBr₄(thf) fragment. Additionally each Mo atom is connected to two Cp ligands. This leads to a tetrahedral coordination of the Mo atoms and a octahedral coordination of the Gd ions.     

Fluoride und Fluorosäuren. IV. Kristallstrukturen von Bortrifluorid und seinen 1:1-Verbindungen mit Wasser und Methanol,Hydroxo- und Methoxotrifluoroborsäure

Fluorides and Fluoro Acids. IV. Crystal Structures of Boron Trifluoride and its 1:1 Compounds with Water and Methanol, Hydroxo- and Methoxotrifluoroboric Acid Solid boron trifluoride displays an enantiotropic phase transition α ? β at ?147°C. A further solid phase, γ-BF₃, is metastable or stable only just below the melting point. Its crystal structure was determined. It is monoclinic with space group P2₁/c, eight molecules in the unit cell and the lattice parameters a = 4.779, b = 14.00, c = 7.430 Å, β = 107.60° at ?131°C. Two independent trigonal planar molecules with a mean B? F bond length of 1.287 Å (1.319 Å after correction for thermal motion) form a three-dimensional packing connection with non-parallel molecular planes across intermolecular B···F contacts of in the average 2.690 Å, by which the boron atoms achieve a total coordination of five fluorine atoms with nearly trigonal bipyramidal geometry. — The crystal structures of hydroxotrifluoroboric acid (BF₃OH₂, monoclinic, P2₁/n, Z = 4, a = 7.641, b = 7.957, c = 4.864 Å, β = 94.80 at ?35°C) and methoxotrifluoroboric acid (BF₃O(CH₃)H, orthorhombic, Pbca, Z = 8, a = 7.054, b = 9.390, c = 11.547 Å at ?40°C) display unlimited three-dimensional and one-dimensional linking, respectively, of the molecules by hydrogen bonds O? H···F.     

Ternäre Phasen des Lithiums mit Kupfer und Phosphor

1. The system Li? Cu? P was investigated by phase analysis. The samples were prepared at 500–600°C. The resulting ternary phases were characterized mainly by x-ray investigation. 2. At 560°C the range of homogeneity of Cu ₃ P lies between 25.6–26.7 atomic % P. Cu₃P forms a high-temperature (HT) modifikation, which crystallizes in a hexagonal subcell of the low-temperature (TT) modification (Z = 6): a = 4.09, c = 7.19 Å, c/a = 1.76; Z = 2 at 560°C. The intensities of the HT-powder pattern could be explained by a model in the space group P3 ml—D³_3d, which was deduced from TT-Cu₃P. 3. Li ₂ CuP , which can be derived from Li₃P, crystallizes hexagonally with a = 16.18, c = 7.724 Å; c/a = 0.477; Z = 32. In the structure, copper occupies the Li position with lowest number and coordination. 4. LiCu ₂ P also crystallizes hexagonally with a = 12.08, c = 7.39 Å; c/a = 0.71; Z = 18. In the direction [001] there is a disordered superlattice. The lattice constants of the high-temperature modification of LiCu₂P, which are related to those of HT-Cu₃P, at 520°C are: a = 4.08, c = 7.44 Å; c/a = 1.82; Z = 2. The interpretation of the intensities of the powder patterns did not result in a plain model related to HT-Cu₃P when calculated for the space group P3 m1—D³_3d. 5. LiCu ₂ P ₂ crystallizes tetragonally with a = 3.887, c = 9.554 Å; c/a = 2.46; Z = 2. The structure determination gave the D1₃-type lattice. The space group is No. 139 I4/mmm—D¹⁷_4h, the atoms occupy the following positions: 2 Li in (2a), 4 Cu in (4d) and 4 P in (4e) with z = 0.388. The compound shows P₂ groups parallel to [001] with a P? P distance of 2.14 Å. 6. Li _1,75 Cu _1,25 P ₂ crystallizes orthorhombically with a = 3.874, b = 12.668, c = 8.743 Å; Z = 6. The crystal structure has been determined. The atoms occupy the following positions within the space group No. 71 Immm—D¹⁵_2h: 2 Li in (2a), 4 Li in (4g) with y = 0.27, 4 Li in (4j) with z = 0.33, 7.5 Cu in (8l) with y = 0.127 and z = 0.267, 8 P in (8l) with y = 0.352 and z = 0.377, and 4 P in (4h) with y = 0.085. This structure, too, is dominated by the occurence of P₂ groups, which are oriented as well parallel [001] as parallel [010].     

CuSeTeCl,CuSeTeBr und CuSeTeI: Verbindungen mit geordneten [SeTe]-Schrauben

CuSeTeCl, CuSeTeBr, and CuSeTeI: Compounds with ordered [SeTe] Screws The hitherto unknown copper(I) chalcogen halides CuSeTeCl, CuSeTeBr and CuSeTeI have been prepared and their crystal structures were determined. The compounds of general composition CuSeTeX crystallize in the monoclinic system, space group P2₁/n (No. 14), Z = 4, a = 7.9796(9), b = 4.7645(8), c = 10.843(3) Å, β = 104.12(1)°, V = 399.8(1) ų (X = Cl), a = 8.155(3), b = 4.765(2), c = 11.286(4) Å, β = 104.21(3)°, V = 425.1(3) ų (X = Br) and a = 8.4370(9) b = 4.7652(5), c = 11.996(2) Å, β = 103.178(9)°, V = 469.6(1) ų (X = I). The crystal structures show infinite onedimensional screws YY′ of chalcogen atoms, with Y = Se and Y′ = Te alternately. The coordinations of Se and Te in these compounds are quite different.     

Drei neue Selenoborato-closo-dodekaborate: Synthesen und Kristallstrukturen von Rb8[B12(BSe3)6], Rb4Hg2[B12(BSe3)6] und Cs4Hg2[B12(BSe3)6]

Three Novel Selenoborato- closo -dodecaborates: Syntheses and Crystal Structures of Rb₈[B₁₂(BSe₃)₆], Rb₄Hg₂[B₁₂(BSe₃)₆], and Cs₄Hg₂[B₁₂(BSe₃)₆] The three selenoborates Rb₈[B₁₂(BSe₃)₆] (P1, a = 10.512(5) Å, b = 10.450(3) Å, c = 10.946(4) Å, α = 104.53(3)°, β = 91.16(3)°, γ = 109.11(3)°, Z = 1), Cs₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.860(2) Å, b = 10.740(2) Å, c = 11.078(2) Å, α = 99.94(3)°, β = 90.81(3)°, γ = 115.97(3)°, Z = 1), and Rb₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.593(2) Å, b = 10.458(2) Å, c = 11.131(2) Å, α = 99.25(3)°, β = 91.16(3)°, γ = 116.30(3)°, Z = 1) were prepared from the metal selenides, amorphous boron and selenium by solid state reactions at 700 °C. These new chalcogenoborates contain B₁₂ icosahedra completely saturated with six trigonal-planar BSe₃ entities functioning as bidentate ligands to form a persubstituted closo-dodecaborate anion. The two isotypic compounds Rb₄Hg₂[B₁₂(BSe₃)₆] and Cs₄Hg₂[B₁₂(BSe₃)₆] are the first selenoborate structures containing a transition metal which are characterized by single crystal diffraction.     

Neue Alkalimetallchromchalkogenide und ihre Struktursystematik

New Alkali Metal Chromium Chalcogenides and their Structural Classification The compounds RbCr₃S₅, K₃Cr₁₁S₁₈, RbCr₅Se₈ and CsCr₅Se₈ could be obtained in the form of wellshaped crystals via fusion reactions of the alkali metal carbonates with chromium and the corresponding chalcogen. The compounds crystallize in the monoclinic space groups C2/m (RbCr₃S₅: a = 19.372(3) Å, b = 3.498(1) Å, c = 12.119(2) Å, β = 122.78(1)°, Z = 4; K₃Cr₁₁S₁₈: a = 41.876(3) Å, b = 3.463(1) Å, c = 16.315(3) Å, β = 150.07(1)°, Z = 2; RbCr₅Se₈: a = 18.737(2) Å, b = 3.623(1) Å; c = 9.016(1) Å, β = 104.65(1)°, Z = 2; CsCr₅Se₈: a = 18.795(2) Å, b = 3.637(1) Å, c = 9.104(1) Å, β = 104.52(1)°, Z = 2). We propose a structure classification from group-subgroup-relations. MAPLE calculations reveal that the reactions of the binary chalcogenides to yield the ternary compounds are exothermic in each case and are dependent on the chromium/alkali metal ratio in the ternary chalcogenides.     

Synthesis,Characterization, and Crystal Structures of a New Coordination Polymer of Manganese(II) Containing Dimethyl Phosphate

The reaction of MnCl₂ with TMP (TMP = Trimethyl phosphate) in THF (THF = tetrahydroforan), led to the coordination polymer [Mn₂(μ₃‐DMP)₂(μ‐DMP)₂]_n (1) (DMP = dimethyl phosphate). This complex was characterized by elemental analysis, IR spectroscopy and single‐crystal structure of 1 . Crystal data for 1 at ?173 °C: triclinic, space group , a = 9.7071(11), b = 10.4482(11), c = 10.6242(11) Å, α = 88.892(2)°, β = 80.829(2)°, γ = 87.572(2)°, Z = 2, R1 = 0.0441.     

Monosubstituted Trinuclear and Tetranuclear VIB Metal Carbonyl Complexes: Syntheses of [{M(CO)5}3(Pf-Pf-Pf)] [Pf-Pf-Pf = PhP(CH2CH2PPh2)2] and [{M(CO)5}4(P-Pf3)] [P-Pf3 = P(CH2CH2PPh2)3] (M = Cr,Mo) and Crystal Structures of the Latter Three

The triligate trimetallic complexes, [{M(CO)₅}₃(Pf-Pf-Pf)] and tetraligate tetrametallic complexes, [{M(CO)₅}₄(P-Pf₃)] (M = Cr and Mo), were prepared from [M(CO) ₆] and the corresponding ligands in MeCN/CH₂Cl₂ promoted by Me₃NO at 0 °C. Crystals of trimer lb are monoclinic, space group P 2₁/n, with a = 13.407(3), b = 15.002(5), c = 26.52(1) Å, β = 90.65(2)°, Z = 4, and R = 0.060 for 2760 observed reflections. Crystals of tetramer 2a are monoclinic, space group P 2₁/c, with a – 14.183(8), b = 29.880(4), c = 16.103(2) Å, β = 94.98(3)°, Z = 4, and R = 0.039 for 5014 observed reflections. Crystals of 2b are monoclinic, space group C 2/c, with a = 42.120(8), b = 13.679(1), c = 23.486(2) Å, β = 92.14(1)°, Z = 8, and R = 0.032 for 6897 observed reflections. Each phosphorus atom of the ligands is coordinated to the M(CO)₅ moiety in each title compounds. The geometry of the four metals is a distorted tetrahedron for the tetramers.     

Hydrothermal Synthesis of Rare Earth Iodates from the Corresponding Periodates: Structures of Sc(IO3)3, Y(IO3)3 · 2 H2O,La(IO3)3 · 1/2 H2O and Lu(IO3)3 · 2 H2O

Hydrothermal syntheses of single crystals of rare earth iodates, by decomposition of the corresponding periodate, are presented. This appears to be a generic method for making rare earth iodate crystals in a short period of time. Single crystal X‐ray diffraction structures of the four title compounds are presented. Sc(IO₃)₃: Space group R3, Z = 6, lattice dimensions at 100 K; a = b = 9.738(1), c = 13.938(1) Å; R₁ = 0.0383. Y(IO₃)₃ · 2 H₂O: Space group P1, Z = 2, lattice dimensions at 100 K: a = 7.3529(2), b = 10.5112(4), c = 7.0282(2) Å, α = 105.177(1)°, β = 109.814(1)°, γ = 95.179(1)°; R₁ = 0.0421. La(IO₃)₃ · ? H₂O: Space group Pn, Z = 2, lattice dimensions at 100 K: a = 7.219(2), b = 11.139(4), c = 10.708(3) Å, β = 91.86(1)°; R₁ = 0.0733. Lu(IO₃)₃ · 2 H₂O: Space group P1, Z = 2, lattice dimensions at 120 K: a = 7.2652(9), b = 7.4458(2), c = 9.3030(3) Å, α = 79.504(1)°, β = 84.755(1)°, γ = 71.676(2)°; R₁ = 0.0349.     

Cu3SbS3: Zur Kristallstruktur und Polymorphie

Cu₃SbS₃: Crystal Structure and Polymorphism The hitherto unknown crystal structure of β-Cu₃SbS₃ at room temperature could be determined from a twinned crystal. The compound crystallizes in the monoclinic system, space group P2₁/c (No. 14), with a = 7.808(1), b = 10.233(2) and c = 13.268(2) Å, β = 90.31(1)°, V = 1 060.1(2) ų, Z = 8. An Extended-Hückel-Calculation shows weak bonding interactions between copper atoms which are coordinated trigonal planar. At ?9°C a first order phase transition occurs and the crystals disintegrate. The low-temperature modification (γ) crystallizes in the orthorhombic system with a = 7.884(2), b = 10.219(2) and c = 6.623(2) Å, V = 533.6(2) ų (?100°C). At 121°C a phase transition of higher order is observed. The high-temperature polymorph (α) of Cu₃SbS₃ is orthorhombic again. From high-temperature precession photographs the space groups Pnma (No. 62) or Pna2₁ (No. 33) can be derived. The lattice constants at 200°C are a = 7.828(3), b = 10.276(4) and c = 6.604(3) Å, V = 531.2(2) ų.     

Synthesis and structural studies of early transition metalloporphyrin complexes. 1. X-ray structures of meso-5,10,15,20 tetratolyl hafnium(IV) μ-dioxo dimer complex and meso-5,10,15,20 tetratolyl porphyrin vanadium(IV) oxo complex

Abstract

(TTP) hafnium dichloride, 1, where TTP = meso-5,10,15,20 tetratolyl porphyrin dianion, has been synthesized and spectroscopically characterized as a precursor to 2. Hydrolysis of 1 gives (TTP) hafnium μ-dioxo dimer, 2. (TTP) vanadium oxo complex, 3, can be obtained by hydrolysis of the corresponding chloro complex. Compound 2 has been characterized by spectroscopic and single crystal X-ray diffraction analyses. [(TTP)HfO]₂-toluene crystalizes in the space group C2/c, a = 31.906(6) Å, b = 16.864(3) Å, c = 19.180(4) Å, β = 117.52(3)°, V = 9152(3) ų, d_calcd = 1.369 g/cm³, Z = 8, 6029 unique observed reflections, final R = 0.077. The Hf atom is 1.02 Å from the plane of the porphyrin ring; Hf-O bond lengths are 2.1 Å. The hafnium atoms are 3.06(1) Å from each other and the average Hf-O-Hf angle is 94°. The porphyrin rings are 5.4° from being parallel and the distance between the centers of the porphyrin rings is ～ 5.1 Å. TTPVO·mesitylene, 3, crystallizes from mesitylene in the space group P1, a = 8.365(2), b = 10.320(3), c = 14.380(5) Å, α = 91.91(3), β = 91.44(3), γ = 108.26(2)°, V = 1177.2(6) ų, d_calcd = 1.27 g/cm³, Z = 1, 1851 observed unique reflections, final R = 0.069. The average V - N distance = 2.016 Å. The coordination geometry around the vanadium is distorted C_4V. The V = O group is disordered about the center of inversion. The vanadium atom resides 0.57 Å above the plane of the nitrogens. The (ring center) -V = O angle is 165.9° while the V = O vector is essentially colinear with the vector normal to the plane of nitrogens.     

Die Reaktionen von M[BF4] (M = Li,K) und (C2H5)2O·BF3 mit (CH3)3SiCN. Bildung von M[BFx>(CN)4—x] (M = Li,K; x = 1, 2) und (CH3)3SiNCBFx(CN)3—x, (x = 0, 1)

The Reactions of M[BF₄] (M = Li, K) and (C₂H₅)₂O·BF₃ with (CH₃)₃SiCN. Formation of M[BF_x(CN)_4—x] (M = Li, K; x = 1, 2) and (CH₃)₃SiNCBF_x(CN)_3—x, (x = 0, 1) The reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BF_x(CN)_4—x] (x = 1, 2; M = Li, K). By using (C₂H₅)₂O·BF₃ the synthesis yields the compounds (CH₃)₃SiNCBF_x(CN)_3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF₂(CN)₂]·2Me₃SiCN Cmc2₁, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) ų, Z = 12, R₁ = 4.7%; K[BF₂(CN)₂] P4₁2₁2, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) ų, Z = 48, R₁ = 2.5%; K[BF(CN)₃] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) ų, Z = 2, R₁ = 3.6%; Me₃SiNCBF(CN)₂ Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) ų, Z = 8, R₁ = 4.4%     

Synthese,Struktur und Reaktionen von Vanadiumsäureestern VO(OR)3: Umesterung und Reaktion mit Oxalsäure

Synthesis, Structure, and Reactions of Vanadium Acid Esters VO(OR)₃: Transesterification and Reaction with Oxalic Acid The reaction of tert.‐Butyl Vanadate VO(O‐tert.Bu)₃ ( 1 ) with H₂C₂O₄ in the primary alcohols ethanol and propanol results in the formation of (ROH)(RO)₂OV^V(C₂O₄)V^VO(OR)₂(HOR) (with R = C₂H₅ 2 and R = C₃H₇ 3 ). Compounds 2 and 3 are the first structurally characterized neutral, binuclear oxo‐oxalato‐complexes with pentavalent vanadium. The two vanadium atoms are connected by a bisbidentate oxalate group. The {VO₆} coordination at each vanadium site is completed by a terminal oxo group, an alcohol ligand and two alcoxide groups. The binuclear molecules are connected to chains by hydrogen bonding. In the case of 2 a reversible isomorphic phase transition in the temperature range of –90 °C to –130 °C is observed. From methanolic solution the polymeric Methyl Vanadate [VO(OMe)₃] ( 4 ) was obtained by transesterification. A report on the crystal structures of 1 , 2 and 3 as well as a redetermination of the structure of 4 is given. Crystal data: 1, orthorhombic, Cmc2₁, a = 16.61(2) Å, b = 9.274(6) Å, c = 10.784(7) Å, V = 1662(2) ų, Z = 4, d_c = 1.144 gcm^–1; 2 (–90 ° C) , monoclinic, I2/a, a = 33.502(4) Å, b = 7.193(1) Å, c = 15.903(2) Å und β = 143.060(3)°, V = 2303(1) ų, Z = 4, d_c = 1.425 gcm^–1; 2 (–130 ° C) , monoclinic, I2/a, a = 33.274(4) Å, b = 7.161(1) Å, c = 47.554(5) Å, β = 142.798(2)°, V = 6851(1) ų, Z = 12, d_c = 1.438 gcm^–1; 3 , triklinic, P1, a = 9.017(5) Å, b = 9.754(5) Å, c = 16.359(9) Å, α = 94.87(2)°, β = 93.34(2)°, γ = 90.42(2)°, V = 1431(1) ų, Z = 2, d_c = 1.340 gcm^–1; 4 , triklinic, P1, a = 8.443(2) Å, b = 8.545(2) Å, c = 9.665(2) Å, α = 103.202(5)°, β = 96.476(5)°, γ = 112.730(4)°, V = 610.2(2)ų, Z = 4, d_c = 1.742 gcm^–1.     

Kristallstruktur,Phasenumwandlung und Kaliumionenleitfähigkeit von Kaliumtrifluormethylsulfonat

Crystal Structure, Phase Transition, and Potassium Ion Conductivity of Potassium Trifluoromethanesulfonate According to the results of temperature dependent powder diffractometry (Guinier‐Simon‐technique) potassium trifluoromethanesulfonate is dimorphic. The phase transition occurs between –63 °C and –45 °C. The low‐temperature modification crystallizes monoclinic with a = 10.300(3) Å, b = 6.052(1) Å, c = 14.710(4) Å, β = 111.83(2)° (–120 °C) and the room‐temperature modification with a = 10.679(5) Å, b = 5.963(2) Å, c = 14.624(5) Å, β = 111.57(3)°, Z = 6, P2₁. According to single crystal structure determination, potassium trifluoromethanesulfonate consists of three different potassium‐oxygen‐coordination polyhedra, linked by sulfur atoms of the trifluoromethanesulfonate groups. This results in a channel structure with all lipophilic trifluoromethane groups pointing into these channels. By means of DSC, the transition temperature and enthalpy have been determined to be –33 °C and 0.93 ± 0.03 kJ/mol, respectively. The enthalpy of melting (237 °C) for potassium trifluoromethanesulfonate is 13.59 kJ/mol, the potassium ionic conductivity is 3.68 · 10^–6 Scm^–1 at 205 °C.     

Darstellung und Kristallstruktur der Addukte [DB-18C6] · CH3CN · CH3CSOH und [DC-18C6](CH3CSOH)2 sowie der salzartigen Verbindungen [Cs(B-15C5)2]CH3CSS und [Cs(DB-18C6)]2S5(DMF)21)

Synthesis and Crystal Structure of the Adducts [DB-18C6] · CH₃CN · CH₃CSOH and [DC-18C6](CH₃CSOH)₂ as well as of the Salt-like Compounds [Cs(B-15C5)₂]CH₃CSS and [Cs(DB-18C6)]₂S₅(DMF)₂¹) The reaction products of crown ethers, cesium, and sulfur in aprotic solvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH₃CN as a solvent, sometimes neutral host-guest adducts crystallize only, e.g., [dibenzo-18C6] · CH₃CN · CH₃CSOH (monoclinic, S. G. P2₁/c, Z = 4, a = 9.73(1) Å, b = 22.03(1) Å, c = 11.86(1) Å, β = 91.8(1)°) or [dicyclohexyl-18C6](CH₃CSOH)₂ (monoclinic, S. G. P2₁/n, Z = 2, a = 7.75(1) Å, b = 10.32(1) Å, c = 17.73(1) Å, β = 95.7(1)°). The monothioacetic acid, CH₃CSOH, must be regarded as the first product of the hydrolysis of CH₃CN. Furthermore, another product of this kind of hydrolysis, CH₃CSSH, is obtained too. Therefore, we also obtain the salt-like compound [Cs(benzo-15C5)₂]CH₃CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Å, b = 16.73(1) Å, c = 13.11(1) Å, β = 106.3(1)°). If the solvent DMF is used, the pentasulfide [Cs(dibenzo-18C6)]₂S₅(DMF)₂ crystallizes (monoclinic, S. G. P2₁/n, Z = 4, a = 14.79(1) Å, b = 14.24(1) Å, c = 25.74(1) Å, β = 92.7(1°. The S₅^2? anions show the cis-conformation.