Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.     

Characterization of [ReO(Tetramethylthiourea)4](PF6)3 in Solution: Electrochemical,NMR and Ligand Substitution Studies

The complex [ReO(Me₄tu)₄]³⁺, with Me₄tu = tetramethylthiourea, is characterized in nonaqueous media. Its structure is studied in acetonitrile solution by ¹H and ¹³C NMR and its electrochemical behavior in the same solvent is analyzed by means of cyclic voltamperometric measurements. Heteronuclear correlation and variable temperature NMR experiments suggest that the complex ion shows a similar structure in solution and in the solid state. At low temperatures (below 0°C) free rotation of the dimethylamine groups around the thiocarbonyl carbon-nitrogen bond is restricted and the dissolved complex adopts the rigid structure observed in the solid state. Cyclic voltamperometric results suggest that the redox behavior of this compound can be explained through an E_rC_iE_r mechanism (a chemical reaction coupled between two electron-transfer reactions). An initial one electron reduction of the complex from Re(V) to Re(IV) followed by an irreversible chemical reaction, leads to a new electroactive species of Re(IV)*, which is reduced to Re(III). The ability of [ReO(Me₄tu)₄](PF₆)₃ to serve as a precursor for other Re(V) complexes by ligand substitution is established, in acetone solution, with different kinds of incoming ligands: diethyldithiocarbamate (Et₂dtc), ethylenediamine (en) and pyridine (py). The previously known complexes [Re^v ₂O₃(Et₂dtc)₄], [Re^VO₂(en)₂](PF₆) and [Re^VO₂(py)₄](PF₆) are easily synthesized under mild conditions with high yields.     

Synthesis and Crystal Structure of a Novel Dinuclear Copper(II) Complex, [Cu2(phen)2(H2O)2(OH)2](HCO3)2 · 6 H2O with phen = 1,10‐phenanthroline

Dark blue plate‐like crystals of [Cu₂(phen)₂ · (H₂O)₂(OH)₂](HCO₃)₂ · 6 H₂O were obtained from a CH₃OH–H₂O solution containing CuCl₂, 1,10‐phenanthroline (phen), sebacic acid and Na₂CO₃. The crystal structure (triclinic, P 1 (no. 2), a = 8.118(1), b = 9.624(1), c = 10.536(1) Å, α = 81.35(1)°, β = 88.51(1)°, γ = 75.77(1)°, Z = 1, R = 0.0332, wR² = 0.0981 for 4163 observed reflections (F ≥ 2σ(F ) out of 4595 unique reflections) consists of divalent [Cu₂(phen)₂(H₂O)₂(OH)₂]²⁺ complex cations, anionic (HCO₃)₂^2– dimers and H₂O molecules. The divalent complex cations (d(Cu…Cu) = 2.905(1) Å) are centered at inversion centers. The Cu atoms are fivefold square‐pyramidally coordinated by two nitrogen and three oxygen atoms from one bidentate chelating phen ligand, two bridging hydroxide groups and one axial water molecule (d(Cu–N)phen = 2.021(2), 2.024(2) Å; d(Cu–O)_OH = 1.941(1), 1.949(1) Å; d(Cu–O)_H2O = 2.254(2) Å). The divalent complex cations are stacked to form 2 D layers parallel (001) with 1 D π‐π stacking interactions along [100] via the terminal phen rings. The dimeric (HCO₃)₂^2– anions and the hydrogen bonded H₂O molecules are sandwiched between the 2 D layers.     

Synthesis and Crystal Structures of the Novel Tetrameric Nitrido Complexes [{cyclo-ReN}4(S2CNEt2)6(MeOH)2(PPh3)2][BPh4]2 · CH2Cl2 · 2 H2O and [{cyclo-ReN}4(S2CNEt2)4Cl4(PMe2Ph)4] · 2 acetone

Novel tetrameric rhenium(V) complexes have been prepared from [ReNCl₂(PPh₃)₂] and [ReN(PMe₂Ph)(S₂CNEt)₂], respectively. [ReNCl₂(PPh₃)₂] reacts with 1.5 equivalents of KS₂CNEt₂ in methanol to yield the unusual dark red species [{cyclo-ReN}₄(S₂CNEt₂)₆(MeOH)₂(PPh₃)₂][BPh₄]₂ · CH₂Cl₂ · 2 H₂O ( 1 ). The crystal structure of the tetramer (triclinic, space group P1, a = 13.842(2), b = 15.213(2), c = 16.796(3) Å, α = 67.88(1), β = 70.90(1), γ = 88.05(1)°, U = 3080.2(8) ų, Z = 1) shows four rhenium atoms in a square configuration which are bridged via linear asymmetric Re≡N–Re groups with bond lengths of about 169 and 203 pm. The molecule contains a centre of symmetry with two distinct octahedral rhenium environments. The first rhenium environment contains two bidentate dithiocarbamate ligands which complete the octahedral geometry and the second contains a bidentate dithiocarbamate ligand, coordinated methanol and has retained a single phosphine coligand. A symmetric compound containing the {cyclo-ReN}₄ core is obtained from the reaction of [ReN(PMe₂Ph)(S₂CNEt₂)₂] with Al₂Cl₆ in acetone. [{cyclo-ReN}₄(S₂CNEt₂)₄Cl₄(PMe₂Ph)₄] · 2 acetone ( 2 ) forms red crystals (monoclinic, space group C2/c, a = 21.432(6), b = 13.700(3), c = 28.060(9) Å, β = 102.37(1)°, U = 8048(4) Å3, Z = 4) with each rhenium atom coordinated by a bidentate dithiocarbamato, a phosphine and a chloro ligand. The non-planar 8-membered {ReN}₄ ring contains asymmetric Re≡N–Re bridges (mean values: 1.69 Å and 2.029 Å, respectively). In contrast, reaction of [ReNCl(S₂CNEt₂)(PMe₂Ph)₂] with one equivalent of K[S₂CN(Me)CH₂CH₂NMe₃]I gave the mixed dithiocarbamato-cation [ReN(S₂CNEt₂)(S₂CN(Me)CH₂CH₂NMe₃)(PMe₂Ph)]⁺ ( 3 ) which was isolated as a tetraphenylborate salt.     

Synthese und Struktur von [Re(NH)Cl2(PMe2Ph)3][TaCl6] und [(Me2PhP)3Cl2Re≡N]2VOCl2

Synthesis and Structure of [Re(NH)Cl₂(PMe₂Ph)₃][TaCl₆] and [(Me₂PhP)₃Cl₂Re≡N]₂VOCl₂ The products of the reaction of ReNCl₂(PMe₂Ph)₃ with TaCl₅ are dependent on the solvent. In CH₂Cl₂ the solvent protonates the nitrido ligand to yield [Re(NH)Cl₂(PMe₂Ph)₃][TaCl₆] as air-stable, reddish brown needles with the space group P2₁/n and a = 1213.8(3), b = 1358.0(2), c = 2165.9(4) pm, β = 92.88(1)°, Z = 4. The Re atom of the cation exhibits an octahedral coordination with the phosphine ligands in meridional arrangement. The imido ligand is in trans-position to a Cl atom with a distance Re–N = 170.4(4) pm. When the reaction is carried out in toluene the dinuclear nitrido complex [Re(NTaCl₅)Cl₂(PMe₂Ph)₃] is obtained instead. The reaction of ReNCl₂(PMe₂Ph)₃ with VCl₃(THF)₃ in toluene affords the threenuclear complex [Re₂N₂Cl₄(PMe₂Ph)₅]VCl₃, which upon crystallization at air gives air-stable, reddish-brown crystals of [(Me₂PhP)₃Cl₂ReN]₂VOCl₂. They crystallize in the monoclinic space group P2₁ with a = 1519.2(5), b = 1257.1(1), c = 1564.3(6) pm, β = 102.86(2)°, and Z = 2. The threenuclear complex shows an almost linear arrangement Re≡N–V–N≡Re with distances Re–N 171(2) pm and V–N of 209(2) pm.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

Syntheses,Structures, and Properties of the Complexes [Ag(N∧S)n](X), N∧S = 1‐Methyl‐2‐(alkylthiomethyl)‐1H‐benzimidazoles,X = PF6 (n = 2) or PO2F2 (n = 1)

The complexes [Ag(η²‐N∧S)₂](PF₆), N∧S = 1‐methyl‐2‐(methylthiomethyl)‐1H‐benzimidazole, mmb (complex 1 ) or 1‐methyl‐2‐(tert‐butylthiomethyl)‐1H‐benzimidazole, mtb (complex 2 ), and [Ag(μ,η²‐mmb)(μ,η²‐O₂PF₂)] (complex 3 ) were synthesized and characterized by X‐ray crystallography. Long Ag–S (ca. 2.70 Å) and shorter Ag–N bonds (ca. 2.23 Å) are part of characteristically distorted tetrahedral coordination arrangements at the silver(I) ions in 1 and 2 . Unexpectedly, the comparison with the copper analogue [Cu(η²‐mmb)₂](PF₆) reveals a more tetrahedral and less linear coordination arrangement for the corresponding silver species. Compound 3 as obtained by hydrolysis of the PF₆ ion or by the use of AgPO₂F₂ exhibits bridging mmb and η²‐difluorophosphate ligands in a chain‐type structure.     

Synthese und Kristallstrukturen der heteronuklearen Nitrido‐Komplexe [(Me2PhP)3(MeCN)ClRe≡N–MCl5] mit M = Sn und Zr

Synthesis and Structures of the Dinuclear Nitrido Complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] with M = Sn and Zr The water sensitive complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] (M = Sn ( 1 ) und Zr ( 2 )) are obtained in dichloromethane from [ReNCl₂(PMe₂Ph)₃] and the acetonitrile adducts of SnCl₄ or ZrCl₄. The compounds crystallize as dichloromethane solvate isotypically with [(Me₂PhP)₃(MeCN)ClRe≡N–TiCl₅] · CH₂Cl₂ in the space group P2₁/n. From toluene crystallize monoclinic crystals of 1 · MeCN · C₇H₈. In the diamagnetic complexes 1 and 2 an anion [MCl₅]^– coordinates to the nitrido ligand of the cationic complex [ReNCl(MeCN)(PMe₂Ph)₃]⁺. The resulting nitrido bridges Re≡N–M are almost linear and asymmetric with Re–N = 169.5 pm, Sn–N = 230.1 pm and Re–N–Sn = 164.5° for 1 and Re–N = 168.4 pm, Zr–N = 237.2 pm and Re–N–Zr = 165.6° for 2 . The phosphine ligands at the Re atom are in a meridional arrangement.     

[Co7(μ4‐O)2(O2C–CH3)8(NCO)2(HNPEt3)4] · 2 OEt2, ein siebenkerniger Komplex mit vier‐, fünf‐ und sechsfach koordinierten Cobalt‐Atomen

[Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂(HNPEt₃)₄] · 2 OEt₂, a Seven Nuclearity Complex with Four, Five, and Sixfold Coordinated Cobalt Atoms The title compound was prepared from cobalt(II) acetate with Me₃SiNPEt₃ at 180 °C and subsequent crystallization from diethylether to give blue, moisture sensitive single crystals, which were characterized by a crystal structure determination. Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1544.0(1), b = 1522.1(2), c = 1702.0(1) pm, β = 103.911(10)°, R = 0.0490. [Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂ · (HNPEt₃)₄] has a centrosymmetric cluster‐like structure in which the octahedrally coordinated central cobalt atom is connected with the remaining six cobalt atoms via two μ₄‐oxygen atoms as well as via four bridging acetato groups to form a Co(Co)₆ octahedral skeleton. Four of the peripheric cobalt atoms have a distorted trigonal‐bipyramidal coordination sphere, the other two cobalt atoms are tetrahedrally coordinated. The latter are connected with the nitrogen atoms of the cyanato groups.     

Synthesis,Structures, Ligand Substitution Reactions,and Electrochemistry of the Nitrile Complexes cis‐[Ru(dppm)2Cl(NCR)]+ PF6– (dppm = Bis(diphenylphosphino)methane,R = CH3, C2H5, tBu,Ph)

Isomerically pure nitrile complexes cis‐[Ru(dppm)₂Cl(NCR)]⁺ ( 2 a – d ) are formed upon chloride displacement from cis‐[Ru(dppm)₂Cl₂] ( 1 ) or, alternatively, by ligand substitution from the acetonitrile complex 2 a . This latter approach does also allow for the introduction of pyridine ( 3 a , b ), heptamethyldisilazane ( 4 ) or isonitrile ligands ( 5 ). All complexes are obtained as the configurationally stable cis‐isomers. Only cis‐[Ru(dppm)₂Cl(CN^tBu)]⁺ slowly isomerizes to the trans from. The solid state structures of the CH₃CN, C₂H₅CN and the trans‐^tBuNC complexes were established by X‐ray crystallography. Electrochemical investigations of the nitrile complexes 2 a – d show in addition to a chemically reversible one‐electron oxidation an irrversible reduction step. In CH₂Cl₂ solution, cis‐ and trans‐[Ru(dppm)₂Cl₂] have been identified as the final products of the electrochemically induced reaction sequence.     

[ReO(MPMEP)(BMPBA)][ReO(MPMEP)(BMPBA)]的合成和结构

合成了未见文献报道的[ReO(MPMEP)(BMPBA)][ReO(MPMEP)(BMPBA)]配合物,其 中MPMEP = 1-（2-甲氧基苯基）-4-（2-巯基乙基）哌嗪,BMPBA = N,N-二（2-巯 基乙基）苄胺,并在适当的溶剂中培养出单晶,用X射线单晶衍射法测定了单晶结 构,晶体属三斜晶系,空间群P1,晶胞参数a = 0.93604(19) nm,b = 1.1044(2) nm,c = 1.3823(3) nm;α = 89.19(3)°,β = 74.50(3)°,γ = 75.04(3)° ;Z = 1,V = 1.3281(5) nm~3,μ = 4.836 mm~(-1),F(000) = 677,R = 0. 0403,wR = 0.0673。配合物的两个[ReO(MPMEP)(BMPBA)]部分均采取扭曲的三角双 锥几何结构,基底面由三齿配体的两个硫原子与氧原子构成,三齿配体的一个氮原 子和单齿配体的一个硫原子分别占取两个顶角位置,硫原子的离子化致使配合物呈 电中性。     

Synthesis and Characterization of the 1 : 1-Adducts of In(C6F5)3 with Acetonitrile,Glyme, and DMAP (DMAP = 4-(N,N-dimethylamino)pyridine), and [PNP][In(C6F5)4] (PNP = bis(triphenylphosphinanyliden)immonium) – the Crystal Structure of [PNP][In(C6F5)4]

In(C₆F₅)₃ · CH₃CN and In(C₆F₅)₃ · glyme were synthesized from InCl₃ and Cd(C₆F₅)₂ in CH₃CN or glyme in 43% and 35% yield, respectively. Replacement of CH₃CN or (C₂H₅)₂O by DMAP yielded the corresponding 1 : 1-adduct. [PNP][In(C₆F₅)₄] was best prepared from the corresponding cesium salt which was best synthesized from the reaction of stoichiometric amounts of In(C₆F₅)₃ · CH₃CN, (CH₃)₃ SiC₆F₅ and CsF in good yield. [PNP][In(C₆F₅)₄] crystallizes in the triclinic space group P 1, a = 1104.9(4) pm, b = 1442.4(6) pm, c = 1833.8(8) pm, α = 110.87(2)°, β = 92.04(3)°, γ = 96.55(3)°, Z = 2.     

Darstellung,Strukturen und EPR-Spektren der Rhenium(II)-Nitrosylkomplexe [Re(NO)Cl2(PPh3)(OPPh3)(OReO3)], [Re(NO)Cl2(OPPh3)2(OReO3)] und [Re(NO)Cl2(OPPh3)3](ReO4)

Synthesis, Structures, and EPR-Spectra of the Rhenium(II) Nitrosyl Complexes [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], [Re(NO)Cl₂(OPPh₃)₂(OReO₃)], and [Re(NO)Cl₂(OPPh₃)₃](ReO₄) The paramagnetic rhenium(II) nitrosyl complexes [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], [Re(NO)Cl₂(OPPh₃)₂ · (OReO₃)], and [Re(NO)Cl₂(OPPh₃)₃](ReO₄) are formed during the reaction of [ReOCl₃(PPh₃)₂] with NO gas in CH₂Cl₂/EtOH. These and two other Re^II complexes with 5 d⁵ ”︁low-spin”︁”︁-configuration can be observed during the reaction EPR spectroscopically. Crystal structure analysis shows linear coordinated NO ligands (Re–N–O-angles between 171.9 and 177.3°). Three OPPh₃ ligands are meridionally coordinated in the final product of the reaction, [Re(NO)Cl₂(OPPh₃)₃][ReO₄] (monoclinic, P2₁/c, a = 13.47(1), b = 17.56(1), c = 24.69(2) Å, β = 95.12(4)°, Z = 4). [Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)] (triclinic P 1, a = 10.561(6), b = 11.770(4), c = 18.483(8) Å, α = 77.29(3), β = 73.53(3), γ = 64.70(4)°, Z = 2) and [Re(NO)Cl₂ (OPPh₃)₂(OReO₃)] (monoclinic P2₁/c, a = 10.652(1), b = 31.638(4), c = 11.886(1) Å, β = 115.59(1)°), Z = 4) can be isolated at shorter reaction times besides the complexes [Re(NO)Cl₃(Ph₃P)₂], [Re(NO)Cl₃(Ph₃P) · (Ph₃PO)], and [ReCl₄(Ph₃P)₂].     

A Novel Dinuclear Copper(II) Complex Molecule: Synthesis and Crystal Structure of Cu2(phen)2(H2O)2(C5H6O4)2 with phen = 1,10‐phenanthroline

Blue crystals of Cu₂(phen)₂(H₂O)₂(C₅H₆O₄)₂ were obtained from a CH₃OH–H₂O solution containing CuCl₂, 1,10‐phenanthroline (phen), glutaric acid and Na₂CO₃. The crystal structure (monoclinic, P2₁/c (no. 14), a = 10.271(1), b = 10.595(1), c = 15.585(1) Å, β = 107.105(3)°, Z = 2, R = 0.0328, wR² = 0.1027 for 3376 observed reflections (F ≥ 2σ(F ) out of 3728 unique reflections) is built up of dinuclear Cu₂(phen)₂(H₂O)₂(C₅H₆O₄)₂ complex molecules centered at inversion centers. The Cu atoms are square‐pyramidally coordinated by two nitrogen atoms of one bidentate chelating phen ligand and three oxygen atoms from two bridging glutarate anions and one axial water molecule (d(Cu–N) = 2.018(2), 2.024(2) Å; basal d(Cu–O) = 1.949(2), 1.956(2) Å; axial d(Cu–O) = 2.382(2) Å). Through the π‐π stacking interactions extending in a direction, the complex molecules are interlinked into 2 D layers parallel to the ac plane. The resultant 2 D layers are held together by hydrogen bonds between water molecules and uncoordinated carboxyl oxygen atoms.     

Synthesis and Crystal Structure of [(n5-C5Me5)2Fe2S4](PF6)2

Abstract

The title compound was synthesized by electrochemical oxidation of (η⁵-C₅Me₅)₂Fe₂S₄ and its X-ray crystal structure was determined. A μ₂-S₂ ligand is converted to μ₂-η²-s₂ ligand by the oxidation.     

Die Orientierung der Re2Cl82–‐Ionen in (PPh4)2[Re2Cl8] · 2 L (L = Acetonitril,Dichlormethan)

The Orientation of the Re₂Cl₈^2– Ions in (PPh₄)₂[Re₂Cl₈] · 2 L (L = Acetonitrile, Dichloromethane) (PPh₄)₂[Re₂Cl₈] · 2 MeCN was obtained in small yields from PPh₄Cl and ReCl₅ in the presence of Na₂S₄ or K₂S₅ in acetontrile. Its crystal structure was determined by X‐ray diffraction. The crystals are nearly isotypic with those of (PPh₄)₂[Re₂Cl₈] · 2 CH₂Cl₂. The PPh₄⁺ ions, the solvent molecules, and the chlorine atoms occupy nearly identical positions in both triclinic structures. Nevertheless, 98% of the Re≡Re groups are differently oriented within the slightly elongated Cl₈ cubes surrounding them. The space requirement of the elongated cubes seems to be more important for the orientation than electrostatic forces. The PPh₄⁺ ions form (PPh₄⁺)₂ pairs around inversion centers.     

Kristallstrukturen,spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n‐Bu4N)2[M(ECN)4] (M = Pd,Pt; E = S,Se)

Crystal Structures, Spectroscopic Analysis, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[M(ECN)₄] (M = Pd, Pt; E = S, Se) The reaction of (NH₄)₂[PdCl₄] or K₂[PtCl₄] with KSCN or KSeCN in aqueous solutions yields the complex anions [Pd(SCN)₄]^2–, [Pt(SCN)₄]^2– and [Pt(SeCN)₄]^2–, which are converted into (n‐Bu₄N) salts with (n‐Bu₄N)HSO₄. (n‐Bu₄N)₂[Pd(SeCN)₄] is formed by treatment of (n‐Bu₄N)₂[PdCl₄] with (n‐Bu₄N)SeCN in acetone. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Pd(SCN)₄] (monoclinic, space group P2₁/n, a = 13.088(3), b = 12.481(2), c = 13.574(3) Å, β = 91.494(15)°, Z = 2), (n‐Bu₄N)₂[Pd(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.171(2), b = 12.644(2), c = 13.560(2) Å, β = 91.430(11)°, Z = 2) and (n‐Bu₄N)₂[Pt(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.167(2), b = 12.641(1), c = 13.563(2) Å, β = 91.516(18)°, Z = 2) reveal, that the compounds crystallize isotypically and the complex anions are centrosymmetric and approximate planar. In the Raman spectra the metal ligand stretching modes of (n‐Bu₄N)₂[Pd(SCN)₄] ( 1 ) and (n‐Bu₄N)₂[Pt(SCN)₄] ( 3 ) are observed in the range of 260–303 cm^–1 and of (n‐Bu₄N)₂[Pd(SeCN)₄] ( 2 ) and (n‐Bu₄N)₂[Pt(SeCN)₄] ( 4 ) in the range of 171–195 cm^–1. The IR and Raman spectra are assigned by normal coordinate analysis using the molecular parameters of the X‐ray determination. The valence force constants are f_d(PdS) = 1.17, f_d(PdSe) = 1.17, f_d(PtS) = 1.44 and f_d(PtSe) = 1.42 mdyn/Å. The ⁷⁷Se NMR resonances are 23 for 2 , –3 for 4 and the ¹⁹⁵Pt NMR resonances 549 for 3 and 130 ppm for 4 .     

Synthesis of a re(VI)-catecholato complex by air oxidation of oxorhenium(V)

The complex [Re(ddcat)₃] (H₂ddcat?=?3,5-di-tert-butylcatechol) was prepared by the reaction of either cis-[Re^VO₂I(PPh₃)₂] or (n-Bu₄N)[Re^VOCl₄] with H₂ddcat in toluene in air. X-ray structure determination of the product unequivocally illustrates that the bidentate chelates are in the catecholato rather than the semiquinone form and that the metal has a formal oxidation state of +VI.     

Untersuchungen zur Darstellung von [CpxSb{M(CO)5}2] (Cpx = Cp,Cp*; M = Cr,W)

Investigations of the Synthesis of [Cp^xSb{M(CO)₅}₂] (Cp^x = Cp, Cp*; M = Cr, W) The reaction of CpSbCl₂ with [Na₂{Cr₂(CO)₁₀}] leads to the chlorostibinidene complex [ClSb{Cr(CO)₅}₂(thf)] ( 1 ), whereas the reaction of CpSbCl₂ with [Na₂{W₂(CO)₁₀}] results in the formation of the complexes [ClSb{W(CO)₅}₃] ( 2 ), [Na(thf)][Cl₂Sb{W(CO)₅}₂] ( 3 ), [ClSb{W(CO)₅}₂(thf)] ( 4 ) and [Sb₂{W(CO)₅}₃] ( 5 ). The stibinidene complex [CpSb{Cr(CO)₅}₂] ( 6 ) is obtained by the reaction of [ClSb{Cr(CO)₅}₂] with NaCp, while its Cp* analogue [Cp*Sb{Cr(CO)₅}₂] ( 7 ) is formed via the metathesis of Cp*SbCl₂ with [Na₂{Cr₂(CO)₁₀}]. The products 2 , 3 , 4 and 7 are additionally characterised by X‐ray structure analyses.     

Phosphaniminato‐Komplexe von Rhenium(VII). Synthesen und Kristallstrukturen von [ReO3(NPR3)] (R = Ph,Et) sowie von [ReO(OSiMe3)3(Me3SiNPEt3)]

Phosphoraneiminato Complexes of Rhenium(VII). Syntheses and Crystal Structures of [ReO₃(NPR₃)] (R = Ph, Et) and of [ReO(OSiMe₃)₃(Me₃SiNPEt₃)] The phosphoraneiminato complexes [ReO₃(NPR₃)] with R = Ph ( 1 ) and R = Et ( 2 ) are made from dirhenium heptaoxide and the silylated phosphoraneimines Me₃SiNPR₃. The complexes 1 and 2 as well as the red silanolate [ReO(OSiMe₃)₃(Me₃SiNPEt₃)] ( 3 ), which is formed as a by‐product in the synthesis of 2 , are characterized crystallographically. 1 and 2 are monomeric molecules, in which the phosphoraneiminato ligands NPR₃^– realize short ReN bonds of 179.3 pm ( 1 ) and 178.6 pm ( 2 ), respectively, with large ReNP bond angles of 162.0° ( 1 ) and 160.6° ( 2 ), respectively. In the rhenium(V) complex 3 the oxoligand occupies the apical position of the tetragonal pyramidal coordination of the rhenium atom, while the oxygen atoms of the Me₃SiO^– groups take the basic positions along with the nitrogen atom of the phosphaneimine molecule.