Binukleare Nickel(II)‐Komplexe mit Oxalamidinaten als Brückenliganden: Synthese und Strukturen von Verbindungen mit planarer,tetraedrischer, tetragonal‐pyramidaler und oktaedrischer Koordination

Binuclear Nickel(II) Complexes with Oxalamidinates as Bridging Ligands: Synthesis and Struktures of Compounds with Planar, Tetrahedral, Tetragonal‐pyramidal, and Octahedral Coordination Oxalamidines R¹–NH–C(=NR²–C(=NR²)–NH–R¹ react selectively with Ni(acac)₂ under formation of the planar complexes [(acac)Ni(oxalamidinate)Ni(acac)]. Two crystal structures of the binuclear complexes with R = R′ = Ph ( 1 ) or p‐tolyl ( 2 ) show that the bridging oxalamidinates bind as bidendate ligands at each Nickel(II) atom. In contrast, the more sterically demanding fragment (Ph₃P)NiBr can only coordinate at sterically less demanding oxalamidinates to form complexes of the type [(Ph₃P)NiBr]₂(oxalamidinate) with tetrahedral coordination of Ni^II found by X‐ray analyses. Oxalamidines containing additional donor atoms in the side arms react very different, but in each case under formation of binuclear complexes, such as [(acac)₂Ni]₂( H₂E ) ( 8 ) (with R¹: –(CH₂)₃PPh₂, R²: p‐tolyl) in which the oxalamidine acts as bidentate neutral P,N‐ligand and the Ni^II atom has an octahedral environment. H₂F (with R¹: –(CH₂)₃PPh₂, R²: Mesityl), however, yields the planar complex [(acac)Ni]₂( F ) ( 9 ) with dianionic oxalamidinate under elimination of acetylacetone. There is no coordination of the donor groups of the side arms in the solid state of complex 9 , in contrast to the analogous binuclear complex [(acac)Ni]₂( H ) 10 (R¹: –CH₂–CH₂‐2‐pyridyl, R²: Mesityl). In this complex a distorted tetragonal‐pyramidal coordination of Ni^II is achieved. 2 reacts with an excess of LiCH₃ under elimination of the oxalamidinate to form the cluster compound Li₄(THF)₄Ni₂Me₈ in very good yields, while 9 yields the THF poorer cluster Li₂(THF)₂Li₂Ni₂Me₈ under similar conditions.     

Synthese und Struktur von Tetrachloro[4-tert-butyl-2(diphenylphosphanyl-κP-methyl)phenolato-κO]tantal(V), ein neuartiger TaV-Komplex mit einem chelatisierenden Aryloxyphosphanliganden

Synthesis and Structure of Tetrachloro[4- tert -butyl-2(diphenylphosphanyl-κP-methyl)phenolato-κO]tantalum(V), a Novel Ta^V Complex with a Chelating Aryloxy Phosphane Ligand 4-tert-Butyl-2-(diphenylphosphanylmethyl)anisol ( 1 ) is prepared from 2-chlormethyl-4-tert-butylanisol and potassium diphenylphosphide in very good yields as a novel oxygen-phosphorus compound with potentially hemilabile ligand properties. Compound 1 reacts with tantalum pentachloride under cleavage of methylchloride revealing the complex tetrachloro[4-tert-butyl-2-(diphenylphosphanyl-κP-methyl)phenolato-κO]tantalum(V) ( 2 ) with a distorted octahedrally coordinated tantalum atom and a chelating aryloxy phosphane ligand. Complex 2 crystallizes in the tetragonal, chiral space group P4₁2₁2 with a = 11.719(5), c = 37.95(5) Å, V = 5171(7) ų, Z = 8. ³¹P NMR spectroscopic studies of 2 establish the coordination of the phosphane unit to the Ta^V center in solution.     

Mehrkernige Eisen/Tantal‐ und Tantal‐Komplexe mit Asn‐Liganden

Polynuclear Iron/Tantalum and Tantalum Complexes with As_n Ligands Starting with [Cp@Ta(CO)₄] ( 1 ) (Cp@ = C₅H₃^tBu₂‐1,3) and As₄ or (^tBuAs)₄ ( 2 ) its thermolysis at 190 °C in decalin gives [{Cp@Ta}₂(μ‐η⁴ : η⁴‐As₈)] ( 3 ), which is also formed according to equation (2) in addition to [{Cp@Ta}₃As₆] ( 5 ). The reaction of 1 or [{Cp*(OC)₂Fe}₂] ( 6 ) with 3 affords 5 or [{Cp*Fe}{Cp@Ta}As₅] ( 8 ) demonstrating the use of 3 as As_n source. 8 can also be synthesized from 1 and [Cp*Fe(η⁵‐As₅)] ( 7 ) for which the cothermolysis of 2 and 6 gives a better yield.     

Nickel(I)‐Komplexe mit 1,1′‐Bis(phosphino)ferrocenen als Liganden

Nickel(I) Complexes with 1,1′‐Bis(phosphino)ferrocenes as Ligands The thermically stable monomeric Nickel(I) complexes [(d^tbpf)Ni(acac)] ( 1 ) and [(dⁱppf)NiCl] ( 2 ) were synthesized and characterized by elemental analyses, EPR spectroscopy, and by X‐ray crystal structure analyses of single crystals (d^tbpf: 1,1′‐bis(di‐tertbutylphosphino)ferrocene; dⁱppf: 1,1′‐bis(diisopropylphosphino)ferrocene). 1 is formed by reduction of Ni(acac)₂ with triethylaluminium in the presence of d^tbpf, together with the nickel(0) complex [(d^tbpf)Ni(C₂H₄)]. 1 contains a Ni^I atom surrounded of two O‐ and two P donor atoms in a distorted tetrahedral coordination. 2 was obtained by reduction of [(dⁱppf)NiCl₂] with NaBH₄. In 2 the nickel(I) atom adopts trigonal planar coordination.     

Palladium(II)‐ und Platin(II)‐Komplexe mit dem Antimalariamittel Mefloquin als Liganden

Metal Complexes of Biologically Important Ligands. CXXVI. Palladium(II) and Platinum(II) Complexes with the Antimalarial Drug Mefloquine as Ligand The coordination sites of the antimalarial drug mefloquine (L) were studied. Reactions of the chloro bridged complexes (allyl)Pd(μ‐Cl)₂Pd(allyl) and (R₃P)(Cl)M(μ‐Cl)₂M(Cl)(PR₃) (M = Pd, Pt) with racemic mefloquine give the compounds (allyl)(Cl)Pd(L) ( 1 ), Cl₂(Et₃P)Pt(L) ( 2 ) and Cl₂(Et₃P)Pd(L) ( 3 ) with coordination of the piperidine N atom of mefloquine. In the presence of NaOMe the N,O‐chelate complexes Cl(Et₃P)Pt(L–H⁺) ( 4 ) and Cl(R₃P)Pd(L–H⁺) ( 5 , 6 , R = Et, nBu) were obtained. Protection of the piperidine N atom of mefloquine by protonation allows the synthesis of the complexes Cl₂(Et₃P)Pt(L + H⁺) ( 7 ) in which mefloquine is coordinated via the quinoline N atom. The structures of 2 , 3 and 4 were determined by X‐ray diffraction analysis. In the crystal of 4 pairs of enantiomers are found which are linked by two hydrogen bridges between the amine group and the chloro ligand.     

Tripodale Bis(2,6‐iminophosphoranyl)pyridin‐Liganden: Eisen‐ und Cobalt‐Komplexe mit Potential in der Ethen‐Polymerisation

Tripodal Bis(2,6‐iminophosphoranyl)pyridine Ligands: Iron and Cobalt Complexes with a Potential in Ethene Polymerisation By Staudinger Reaction of bis‐2,6‐diphenylphosphanyl‐pyridine with aryl‐, alkyl‐ and silylazides tripodal ligands L = 2,6‐(Ph₂P=NR)₂C₅H₃N (R = Ph 1 a , Mes 1 b , Ad  1 c , SiMe₃ 1 d ) are synthesized. The reaction of ligand 1 b  with equimolar amounts of [CoCl₂(THF)₂] and [FeCl₂(THF)_1.5] in THF does not lead to the expected neutral complexes [(k³‐L)MCl₂] but to coordination compounds of the composition L₂(CoCl₂)₃ ( 2 a ) und L(FeCl₂)₂ ( 3 ). By using acetonitrile as solvent or by crystallisation of 2 a from hot acetonitrile the cationic complex [(k³‐L)CoCl(MeCN)]Cl ( 2 b ) is formed as a second product. The molecular structure 2 b has been characterized by an X‐ray single crystal structure analysis (triclinic, P1, Z = 2, a = 1299.8(1), b = 1488.8(2), c = 1674.2(2) pm, α = 82.911(13)°, β = 76.715(12)°, γ = 72.758(11)°). A preliminary test with 3 shows, that coordination compounds of the ligand system introduced here have potential as catalysts in methyl alumoxane mediated ethene polymerisation.     

Dinukleare Kupfer(II)‐Komplexe mit chiralen makrocyclischen Liganden vom Schiff‐Basen‐Typ: Synthesen und Strukturen

Complexes with Macrocyclic Ligands. V Dinuclear Copper(II) Complexes with Chiral Macrocyclic Ligands of Schiff‐Base Type: Syntheses and Structures The synthesis and properties of four chiral, dinuclear, macrocyclic, cationic copper(II) complexes, [Cu₂(L^m,n)]²⁺ ( 1 – 4 ), are described. The two symmetrical compounds [Cu₂(L^2,2)][ClO₄]₂ ( 1 and 2 ) were synthesized in a one‐step reaction from 2,6‐diformyl‐4‐tert.‐butylphenol, copper(II)‐perchlorate and the chiral diamine (1S,2S)‐1,2‐diphenylethylenediamine (synthesis of 1 ) and (1R,2R)‐1,2‐diaminocyclohexane (synthesis of 2 ), respectively. For the synthesis of the two unsymmetrical compounds [Cu₂(L^Ph,n)][ClO₄]₂ ( 3 and 4 ) the mononuclear, neutral copper(II) complex [CuL^Ph] ( 5 ) [synthesized from 2,6‐diformyl‐4‐tert.‐butylphenol, copper(II)‐acetate and 1,2‐phenylenediamine] was reacted with (1R,2R)‐1,2‐diaminocyclohexane (synthesis of 3 ) and (S)‐1,1′‐binaphthyl‐2,2′‐diamine (synthesis of 4 ), respectively. The structures of the two unsymmetrical copper(II) compounds ( 3 and 4 ) were determined by X‐ray diffraction.     

Synthesis and Investigation of 1,3‐Bis(5‐nitraminotetrazol‐1‐yl)propan‐2‐ol and its Salts

1,3‐Bis(5‐nitraminotetrazol‐1‐yl)propan‐2‐ol ( 5 ) was prepared by the reaction of 5‐aminotetrazole and 1,3‐dichloroisopropanol under basic conditions. Obtained 1,3‐bis(5‐aminotetrazol‐1‐yl)propan‐2‐ol ( 3 ) was nitrated with 100 % nitric acid. In this context in situ hydrolysis of the nitrate ester was studied. Metal and nitrogen‐rich salts of the neutral compound 5 were prepared and analyzed. Crystal structures of three salts and the sensitivities toward impact, friction and electrostatic discharge were determined as well. The performance values of the compounds were calculated using the EXPLO5 program. A detailed comparison of the different salts is also enclosed.     

Iridium(I)‐ und Iridium(III)‐Komplexe mit Triisopropylarsan als Ligand

Iridium(I) and Iridium(III) Complexes with Triisopropylarsane as Ligand The ethene complex trans‐[IrCl(C₂H₄)(AsiPr₃)₂] ( 2 ), which was prepared from [IrCl(C₂H₄)₂]₂ and AsiPr₃, reacted with CO and Ph₂CN₂ by displacement of ethene to yield the substitution products trans‐[IrCl(L)(AsiPr₃)₂] ( 3 : L = CO; 4 : L = N₂). UV irradiation of 2 in the presence of acetonitrile gave via intramolecular oxidative addition the hydrido(vinyl)iridium(III) compound [IrHCl(CH=CH₂)(CH₃CN)(AsiPr₃)₂] ( 5 ). The reaction of 2 with dihydrogen led under argon to the formation of the octahedral complex [IrH₂Cl(C₂H₄)(AsiPr₃)₂] ( 7 ), whereas from 2 under 1 bar H₂ the ethene‐free compound [IrH₂Cl(AsiPr₃)₂] ( 6 ) was generated. Complex 6 reacted with ethene to afford 7 and with pyridine to give [IrH₂Cl(py)(AsiPr₃)₂] ( 8 ). The mixed arsane(phosphane)iridium(I) compound [IrCl(C₂H₄)(PiPr₃)(AsiPr₃)] ( 11 ) was prepared either from the dinuclear complex [IrCl(C₂H₄)(PiPr₃)]2 ( 9 ) and AsiPr₃ or by ligand exchange from [IrCl(C₂H₄)(PiPr₃)(SbiPr₃)] ( 10 ) und triisopropylarsane. The molecular structure of 5 was determined by X‐ray crystallography.     

Phthalocyaninate und Tetraphenylporphyrinate von hochkoordiniertem ZrIV/HfIV mit Hydroxo‐, Chloro‐, (Di)Phenolato‐, (Hydrogen)Carbonato‐ sowie (Amino)Carboxylato‐Liganden

Phthalocyaninates and Tetraphenylporphyrinates of High Co‐ordinated Zr^IV/Hf^IV with Hydroxo, Chloro, (Di)Phenolato, (Hydrogen)Carbonato, and (Amino)Carboxylato Ligands Crystals of tetra(n‐butyl)ammonium cis‐tri(phenolato)phthalocyaninato(2‐)zirconate(IV) ( 2 ) and ‐hafnate(IV) ( 1 ), di(tetra(n‐butyl)ammonium) cis‐di(tetrachlorocatecholato(O, O')phthalocyaninato(2‐)zirconate(IV) ( 3 ), and cis‐(di(μ‐alaninato(O, O')di(μ‐hydroxo))di(phthalocyaninato(2‐)zirconium(IV)) ( 12 ) have been isolated from tetra(n‐butyl)ammonium hydroxide solutions of cis‐di(chloro)phthalocyaninato(2‐)zirconium(IV) and ‐hafnium(IV), respectively, and the corresponding acid in polar organic solvents. Similarly, with cis‐di(chloro)tetraphenylporphyrinato(2‐)zirconium(IV), ^cis[Zr(Cl)₂tpp] as precursor crystalline tetra(n‐butyl)ammoniumcis‐tetrachlorocatecholato(O, O')hydrogentetrachlorocatecholato(O)tetraphenylporphyrinato(2‐)zirconate(IV) ( 4 ), cis‐hydrogencarbonato(O, O')phenolatotetraphenylporphyrinato(2‐)zirconium(IV) ( 6 ), cis‐di(benzoato(O, O'))tetraphenylporphyrinato(2‐)zirconium(IV) ( 11 ), and cis‐tetra(μ‐hydroxo)di(tetraphenylporphyrinato(2‐)zirconium(IV)) ( 13 ) with a cis‐arrangement of the symmetry equivalent μ‐hydroxo ligands, and from di(acetato)tetraphenylporphyrinato(2‐)zirconium(IV) the corresponding trans‐isomer ( 14 ) have been prepared. The endothermic dehydration at 215 °C of 13/14 yields μ‐oxodi(μ‐hydroxo)di(tetraphenylporphyrinato(2‐)zirconium(IV)) ( 15 ). 15 also precipitates on dilution of a solution of ^cis[Zr(X)₂tpp] (X = Cl, OAc) in dmf/(ⁿBu₄N)OH with water, while on prolonged standing of this solution on air tri(tetra(n‐butyl)ammonium) cis‐(^nido〈di(carbonato(O, O'))undecaaquamethoxide〉tetraphenylporphyrinato(2‐)zirconate(IV) ( 7 ) crystallizes, in which Zr^IV coordinates a supramolecular nestlike ^nido〈(O₂CO)₂(H₂O)₁₁OCH₃〉^5— cluster anion stabilised by hydrogen bonding in a nanocage of surrounding (ⁿBu₄N)⁺ cations. On the other hand, ^cis[Zr(Cl)₂pc] forms with (Et₄N)₂CO₃ in dichloromethane di(tetraethylammonium) cis‐di(carbonato(O, O')phthalocyaninato(2‐)zirconate(IV) ( 5 ). ^cis[Zr(Cl)₂tpp] dissolves in various O‐donor solvents, from which cis‐di(chloro)dimethylformamidetetraphenylporphyrinato(2‐)zirconium(IV) ( 8 ), cis‐di(chloro)dimethylsulfoxidetetraphenylporphyrinato(2‐)zirconium(IV) ( 9 ), and a 1:1 mixture ( 10 ) of cis‐di(chloro)dimethylsulfoxidetetraphenylporphyrinato(2‐)zirconium(IV) ( 10a ) and cis‐chlorodi(dimethylsulfoxide)tetraphenylporphyrinato(2‐)zirconium(IV) chloride ( 10b ) crystallize. All complexes contain solvate molecules in the solid state, except 3 . Zr^IV/Hf^IV is directed by ∼1Å out of the plane of the tetrapyrrolic ligand (pc, tpp) towards the mutually cis‐coordinated axial ligands. In the more concavely distorted phthalocyaninates, Zr^IV is mainly eight‐coordinated and in the tetraphenylporphyrinates seven‐coordinated. The octa‐coordinated Zr atom is in a distorted quadratic antiprism, and the hepta‐coordinated one is in a square‐base‐trigonal‐cap cooordination polyhedron. In most tpp complexes, the Zr atom is displaced by up to 0.3Å out of the centre of the coordination polyhedron towards the tetrapyrrolic ligand. In 13/14 , both antiprisms are face shared by an O₄ plane, and in 12 they are shared by an O₂ edge and the O atoms of the bridging aminocarboxylates, the dihedral angle between the O₄ planes of both antiprisms being 50.1(1)°. The mean Zr‐N_p distance is 0.05Å longer in the pc complexes than in the tpp complexes (d(Zr‐N_p)_pc = 2.31Å). In the monophenolato complexes, the mean Zr‐O distance (∼2.00Å) is shorter than in the complexes with other O‐donor ligands (d(Zr‐O)_pc = 2.18Å; d(Zr‐O)_tpp = 2.21Å); the Zr‐Cl distances vary between 2.473(1) and 2.559(2)Å (d(Zr‐Cl)_tpp = 2.51Å). d(C‐O_exo) = 1.494(4)Å in the bidentate hydrogencarbonato ligand in 6 is 0.26Å longer than in the bidentate carbonato ligands in 5 and 7 . 9 and 10a are rotamers slightly differing by the orientation of the axial ligands with respect to the tpp ligand. In 1—4, 6 , and 11 the phenolato, catecholato, and benzoato ligands, respectively, are in syn‐ and/or anti‐conformations with respect to the plane of the macrocycle. π‐Dimers with modest overlap of the neighbouring macrocyclic rings are observed in 5, 6, 8, 9, 10b, 12 , and 14 . The common UV/Vis spectroscopical and vibrational properties of the new phthalocyaninates and tetraphenylporphyrinates scarcely reflect their rich structural diversity.     

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.     

Synthese und Struktur von Ruthenium(II)‐Komplexen mit Triazenido‐ und Pentaazadienido‐Liganden

Synthesis and Crystal Structure of Ruthenium(II) Complexes with Triazenido and Pentaazadienido Ligands The ruthenium(II) triazenido complex [RuCl(ClC₆H₄N₃C₆H₄Cl)(p‐cymene)] ( 1 ) is obtained by the reaction of silver bis(p‐chlorphenyl)triazenid with [RuCl₂(p‐cymene)]₂ in CH₂Cl₂, and forms air stable, orange yellow crystals. It crystallizes as 1 ·CH₂Cl₂ in the orthorhombic space group Pbca with the lattice parameters a = 3134.3(3), b = 2105.7(2), c = 769.15(4) pm and Z = 8. In the diamagnetic mononuclear complex 1 the chelating triazenido ligand coordinates with the atoms N(1) and N(3). p‐Cymene binds η⁶ with its C₆ ring. The reaction of the etherphosphane complex [RuCl₂(Ph₂PCH₂C₄H₇O₂)₂] with 1, 3‐bis(p‐tolyl)triazenid in THF yields the complex [RuCl(tolyl‐N₃‐tolyl)(Ph₂PCH₂C₄H₇O₂)₂] ( 2 ). 2 forms monoclinic, red crystals with the space group P2₁/c and a = 1521.0(2), b = 1451.8(2), c = 2073.7(2) pm, β = 99.29(1)° and Z = 4. It is air stable and diamagnetic. The triazenide ion coordinates with the atoms N(1) and N(3). One of the two etherphosphane ligands is chelating and coordinates with the P atom and one O atom, while the other ligand binds in a monodentate fashion with its P atom, resulting in a coordination number of six for the Ru^II. [Ag(tolyl‐N₅‐tolyl)]₂ reacts in THF with [RuCl₂(C₆H₆)]₂ to afford the air stable, diamagnetic pentaazadienido complex [RuCl(tolyl‐N₅‐tolyl)(C₆H₆)] ( 3 ). 3 forms monoclinic, red crystals with the space group P2₁/c and a = 1462.4(1), b = 1056.51(8), c = 1371.4(1) pm, β = 114.36(1)° and Z = 4. The chelating pentaazadienido ligand coordinates with the atoms N(1) and N(3) at the divalent Ru atom. The benzene molecule binds η⁶ with its π system.     

Umsetzungen von Cp*NbCl4 und Cp*TaCl4 mit Trimethylsilyl‐azid,Me3Si‐N3. Molekülstrukturen der bis(azido)‐oxo‐verbrückten Komplexe [Cp*NbCl(N3)(μ‐N3)]2(μ‐O) und [Cp*TaCl2(μ‐N3)]2(μ‐O) (Cp* = Pentamethylcyclopentadienyl)

Reactions of Cp*NbCl₄ and Cp*TaCl₄ with Trimethylsilyl‐azide, Me₃Si‐N₃. Molecular Structures of the Bis(azido)‐Oxo‐Bridged Complexes [Cp*NbCl(N₃)(μ‐N₃)]₂(μ‐O) and [Cp*TaCl₂(μ‐N₃)]₂(μ‐O) (Cp* = Pentamethylcyclopentadienyl) The chloro ligands in Cp*TaCl₄ (1c) can be stepwise substituted for azido ligands by reactions with trimethylsilyl azide, Me₃Si‐N₃ (A) , to generate the complete series of the bis(azido)‐bridged dimers [Cp*TaCl_3‐n(N₃)_n(μ‐N₃)]₂ ( n = 0 (2c) , n = 1 (3c) , n = 2 (4c) and n = 3 (5c) ). If the solvent CH₂Cl₂ contains traces of water, an additional oxo bridge is incorporated to give [Cp*‐TaCl₂(μ‐N₃)]₂(μ‐O) (6c) or [Cp*TaCl(N₃)(μ‐N₃)]₂(μ‐O) (7c) , respectively. Both 6c and 7c are also formed in stoichiometric reactions from [Cp*TaCl₂(μ‐OH)]₂(μ‐O) (8c) and A . Analogous reactions of Cp*NbCl₄ (1b) with A were used to prepare the azide‐rich dinuclear products [Cp*NbCl_3‐n(N₃)_n(μ‐N₃)]₂ (n = 2 (4b) , and n = 3 (5b) ), and [Cp*NbCl(N₃)(μ‐N₃)]₂(μ‐O) (7b) . The mononuclear complex Cp*Ta(N₃)Me₃ (10c) is obtained from Cp*Ta(Cl)Me₃ and A . All azido complexes were characterised by their IR as well as their ¹H and ¹³C NMR spectra; X‐ray crystal structure analyses are available for 6c and 7b .     

Mononukleare Kupfer(II)‐Komplexe von dioxaalkylenund alkylenverbrückten Bis‐isoharnstoffen

Mononuclear Copper(II) Complexes of Dioxaalkylene and Alkylene Bridged Bis‐isoureas By reaction of N‐benzoylthiocarbamic‐O,S‐diethylester with primary diamines (oxa)alkylene bridged isoureas 1 have been prepared. They yield with Cu^II neutral chelates 2 with tetradentate ligand coordination. The structures of the ligand 1 a and of the related Cu^II complex 2 a have been determined by X‐ray crystal structure analysis. They show an enamine tautomer in the ligand and a slightly tetrahedrally distorted coordination with an (oxa)alkylene bridge between the trans arranged N ligator atoms in the complex.     

RuS4Cl12 und Ru2S6Cl16, zwei neue Ruthenium(II)‐Komplexe mit SCl2‐Liganden

RuS₄Cl₁₂ and Ru₂S₆Cl₁₆, Two New Ruthenium(II) Complexes with SCl₂ Ligands Ru powder was reacted with SCl₂ in closed silika ampoules at 140 °C. From the black solution three compounds RuS₄Cl₁₂ 1 , Ru₂S₆Cl₁₆ 2 , and Ru₂S₄Cl₁₃ 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) Å, b = 11.63(1) Å, c = 15.495(1) Å, β = 105.23(1)°, space group P2₁/c, z = 4) are identified as Trichlorsulfonium‐tris(dichlorsulfan)trichloro‐ruthenat(II) SCl₃[RuCl₃(SCl₂)₃]. In the structure the complex anions fac‐[RuCl₃(SCl₂)₃]^– and the cations [SCl₃]⁺ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Å, b = 7.997(2) Å, c = 10.708(2) Å, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P‐1, z = 1) contain the binuclear complex Bis‐μ‐chloro‐dichloro‐hexakis(dichlorsulfan)‐diruthenium(II), (SCl₂)₃ClRu(μ‐Cl)₂RuCl(SCl₂)₃ with two fac‐RuCl₃(SCl₂)₃‐units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl₂(SCl₂)Ru(μ‐Cl)₃Ru(SCl₂)₃]. The vibrational spectra and the thermal behaviour of the compounds are discussed.     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von Quecksilber(II)‐bis(tetracyanoborat) Hg[B(CN)4]2 und Diquecksilber(I)‐bis(tetracyanoborat) Hg2[B(CN)4]2

Preparation, Spectroscopic Characterization and Crystal Structures of Mercury(II)‐bis(tetracyanoborate) Hg[B(CN)₄]₂ and Dimercury(I)‐bis(tetracyanoborate) Hg₂[B(CN)₄]₂ Hg[B(CN)₄]₂ ( 1 ) is synthesised by the reaction between Hg(NO₃)₂ and K[B(CN)₄]₂. In a comproportionation reaction of 1 with elemental mercury the corresponding mercury(I) salt Hg₂[B(CN)₄]₂ ( 2 ) is obtained. The compounds were characterised by vibrational‐ and NMR‐spectroscopy, and their crystal structures were determined. Hg[B(CN)₄]₂ crystallizes in the trigonal system in the space group P3¯m1 with a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)ų, and one formula unit per unit cell. For Hg₂[B(CN)₄]₂ an orthorhombic unit cell with a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)Å, and Z = 4 is observed.