Synthese und Struktur von Re4(μ3-Te)4(TeBr2)4Br8

Synthesis and Structure of Re₄(μ₃-Te)₄(TeBr₂)₄Br₈ Re₄(μ₃-Te)₄(TeBr₂)₄Br₈ is obtained from the elements at 550°C in an evacuated glass ampoule. The diamagnetic compound forms air-stable, metallic lustre black crystals crystallizing in the tetragonal space group I4 with a = 1120.2(2), c = 1393.5(3) pm, and Z = 2. The crystal structure is built up by isolated cluster molecules Re₄(μ₃-Te)₄(TeBr₂)₄Br₈ occupying the centres 4 at 1/2, 1/2, 0 and 0, 0, 1/2. The inner sceleton is formed by a Re₄Te₄ heterocubane unit with short Re? Re distances of 277 and 283 pm, which can be discussed as single bonds. Each Re atom coordinates in addition two Br^? ligands and one TeBr₂ molecule. For Re therefore results the oxidation state +IV. Reaction of Re₄(μ₃-Te)₄(TeBr₂)₄Br₈ with I₂ yields (TeI₄)₄.     

Halogenaustausch an Re3-Clustern: Ein neuer Syntheseweg für binäre und ternäre Rhenium(III)-bromide. Kristallstrukturen von Cs2[Re3Br11] und Cs3[Re3Br3Cl9]

Halogen Exchange at Re₃-Clusters: A New Synthetic Route to Binary and Ternary Rhenium(III) Bromides. Crystal Structures of Cs₂[Re₃Br₁₁] and Cs₃[Re₃Br₃Cl₉] The substitution of “inner” ligands in transition metal clusters in aqueous HX solutions is hitherto unknown. For the first time the substitution of bridging and terminal chloride for bromide ions was observed at rhenium clusters, [Re₃(μ-Cl^i,b)₃(Cl)(Cl^i,t)_(3?x)(H₂O^i,t)_x]^(3?x)? (x = 0–3), via the reaction of “ReCl₃ · 2 H₂O” in hot hydrobromic acid solution under an inert gas atmosphere. This establishes a new synthetic route to ternary Re(III) bromides as well as to ReBr₃. However, ternary Re(IV) bromides, A₂ReBr₆ (A = Rb, Cs), are dominating in the presence of oxygen, rhenium(III) bromides are only by-products. Dark brown rods of Cs₂[Re₃Br₁₁] are obtained from argon saturated, hot hydrobromic acid solutions of “ReCl₃ · 2 H₂O” and CsBr. The crystal structure (orthorhombic, Pnma (Nr. 62); a = 955.51(5); b = 1 610.29(10); c = 1 372.70(9); Z = 4; V_m = 318.0(2) cm³mol^?1; R = 0.084, R_w = 0.058) consists of defect clusters [Re₃BrBrBr□^i,t]^2? in which one in plane, terminal position is not occupied. The substitution of “inner” ligands has been observed in the case of chloride for bromide only, the Br^i,b and I^i,b ligands in ReBr₃ and ReI₃, respectively, are not substituted in hydrochloric acid even at temperatures as high as 100°C. Bordeaux red square pyramids of CsReBrCl₃ = Cs₃[Re₃(μ-Br^i,b)₃ClCl] are obtained from hot hydrochloric acid solutions of ReBr₃ · 2/3 H₂O upon evaporation. CsReBrCl₃ (orthorhombic, C2cm (Nr. 40); a = 1 419.0(1); b = 1 419.2(1); c = 1 080.30(8) pm; Z = 4; V_m = 327.6(3) cm³mol^?1; R = 0.033, R_w = 0.028) is isostructural to the corresponding chloride CsReCl₄.     

Kristallstruktur von (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2

Crystal Structure of (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ . (NMe₄)₂[Re₃Br₁₁(H₂O)] [Re₃Br₉(H₂O)₃](H₂O)₂ crystallizes from hydrobromic acid solution of Re₃Br₉ · 2 H₂O and NMe₄Br at 0 – 5°C. The crystal structure (monoclinic; P2₁/m (Nr. 11); a = 967.9(3); b = 1 529.7(4); c = 1 710.9(4) pm; β = 91.66(2)°; Z = 2; R = 0.113; R_w = 0.068) has been determined from four-circle diffractometer data. The structure contains two different cluster units of trivalent rhenium, isolated anionic [Re₃Br₁₁(H₂O)]^2? units and neutral cluster units that are connected through crystal water molecules to chains{[Re₃Br₉(H₂O)₃](H₂O)₂}.     

Gemischtligand-Komplexe des Rheniums. VI. Darstellung und Strukturen der Rhenium?Thionitrosyl-Komplexe mer-[Re(NS)Cl2(Me2PhP)3] · CH2Cl2 und trans-[Re(NS)Cl3(Me2PhP)2]

Mixed-ligand Complexes of Rhenium. VI. Synthesis and X-Ray Structures of the Rhenium Thionitrosyl Complexes mer-[Re(NS)Cl₂(Me₂PhP)₃] · CH₂Cl₂ and trans-[Re(NS)Cl₃(Me₂PhP)₂] mer-Dichlorotris(dimethylphenylphosphine)(thionitrosyl)rhenium(I), mer-[Re(NS)Cl₂(Me₂PhP)₃], and trans-Trichlorobis(dimethylphenylphosphine)(thionitrosyl)rhenium(II), trans-[Re(NS)Cl₃(Me₂PhP)₂], are formed during the reaction of rhenium(V) mixed-ligand complexes of the general formula [ReN(Cl)(Me₂PhP)₂(R₂tcb)] with disulphur dichloride (HR₂tcb = N-(N,N-dialkylthiocarbamoyl)benzamidine). The chelating ligands are substituted during the reaction. mer-[Re(NS)Cl₂(Me₂PhP)₃] crystallizes monoclinic in the space group P2₁/n. The dimensions of the unit cell are a = 8.854(2); b = 31.295(3); c = 11.981(3) Å; β = 108.14(1)°; Z = 4. A final R value of 0.033 was achieved on the basis of 5 387 reflections with I ≥ 3σ(I). The rhenium atom is coordinated in a distorted octahedral environment. The Me₂PhP ligands are arranged meridionally cis to the linear thionitrosyl group. trans-[Re(NS)Cl₃(Me₂PhP)₂] crystallizes in the monoclinic space group C2/c with an unit cell of the dimensions a = 33.320(9); b = 8.446(1); c = 17.28(5) Å; β = 116.09(1)°, Z = 8. The R value converged at 0.026 on the basis of 5 460 independent reflections. The metal is octahedrally coordinated with the phosphine ligands in trans position to each other. The angle Re? N? S is 175.7(3)°.     

Neue mehrkernige Indium–Stickstoff‐Verbindungen – Synthese und Kristallstrukturen von [In4X4(NtBu)4] (X = Cl,Br, I) und [In3Br4(NtBu)(NHtBu)3]

New Polynuclear Indium Nitrogen Compounds – Synthesis and Crystal Structures of [In₄X₄(N^tBu)₄] (X = Cl, Br, I) and [In₃Br₄(N^tBu)(NH^tBu)₃] The reaction of the indium trihalides InX₃ (X = Cl, Br, I) with LiNH^tBu in THF leads to the In₄N₄‐heterocubanes [In₄X₄(N^tBu)₄] (X = Cl 1 , Br 2 , I 3 ). Additionally [In₃Br₄(N^tBu)(NH^tBu)₃] ( 4 ) was obtained as a by‐product in the synthesis of 2 . 1 – 4 have been characterized by x‐ray crystal structure analysis. 1 – 3 consist of In₄N₄ heterocubane cores with an alternating arrangement of In and N atoms. The In atoms are coordinated nearly tetrahedrally by three N‐atoms and a terminal halogen atom. 4 contains a tricyclic In₃N₄ core which can be formally derived from an In₄N₄‐heterocubane by removing one In atom.     

Über Chalkogenidhalogenide des Rheniums: Synthese und Kristallstrukturen der Dreieckscluster Re3E7X7 (E = S,Se; X = Cl,Br)

On Chalcogenide Halogenides of Rhenium: Synthesis and Crystal Structures of the Triangular Clusters Re₃E₇X₇ (E = S, Se; X = Cl, Br) The compounds Re₃E₇X₇ are obtained from rhenium tetrahalides ReX₄, elemental chalcogens and the respective chalcogen halides E₂X₂ or SeX₄ (E = S, Se; X = Cl, Br). Re₃S₇Cl₇, Re₃S₇Br₇ and Re₃Se₇Br₇ are formed in solutions of sulfur or selenium halides or SiBr₄ in form of black crystals and crystallize isotypically in the trigonal space group P31c. Re₃Se₇Cl₇ is formed by solid state reaction of ReCl₄, Se and SeCl₄ or by thermal decomposition of Se₄[ReCl₆], crystallizing as red, in thin layers transparent crystals in the orthorhombic space group Pbcm. The crystal structures consist of discrete positively charged cluster units and halide ions according to the formula [Re₃(μ₃-E)(μ₂-E₂)₃X₆]⁺X^–. In the rhenium triangular clusters the Re–Re distances range from 269,0 to 270,4 pm for the sulfur and from 273,3 to 275,3 pm for the selenium containing compounds. The Re₃ units are capped by chalcogen atoms, three E₂ groups form bridges over the edges of the Re₃ triangles. The trigonal and the orthorhombic structure type show differences in the site symmetry of the clusters (C₃ vs. C_s) and in the stacking sequence of the molecules, which are packed in the motif of a closest packing of spheres.     

Synthese und Kristallstruktur von [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4]

Synthesis and Crystal Structure of [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] Treatment of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] ( 1 ) with hot water produces the dinuclear complex [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] ( 2 ) which could be crystallized from dichloromethane/pentane. 2 crystallizes in the monoclinic space group P2₁/n with a = 835.7(1), b = 1187.8(1), c = 1902.7(1) pm, β = 91.877(5)° and Z = 2. The anion contains a four‐membered Fe—In—Fe—In ring with octahedral environment at the iron atom and tetrahedral coordination at the In atom.     

Synthese und Molekülstruktur von [Li(THF)4][{(CO)4Mo}2(μ-PPh2)(μ-PPh2PPh2)]: Die erste Verbindung mit einem 1,3-Dimetalla-cyclopentaphosphan-Gerüst

Synthesis and Molecular Structure of [Li(THF)₄][{(CO)₄Mo}₂(μ-PPh₂)(μ-PPh₂PPh₂)]: The First Compound with an 1,3-Dimetalla-cyclopentaphosphane Ring [Mo(CO)₄(NBD)] (NBD = norbornadiene) reacts with LiPPh₂ and PPh₂PPh₂ in THF at –80 °C to give [Li(THF)₄][{(CO)₄Mo}₂(μ-PPh₂)(μ-PPh₂PPh₂)] ( 1 ). 1 exhibits an A₂X coupling pattern in the ³¹P NMR spectrum. A crystal structure determination showed the presence of bridging phosphanido (PPh₂) and diphosphane ligands (PPh₂PPh₂). The central Mo₂P₃ five-membered ring adopts a half-chair conformation and thus resembles an inorganic cyclopentane.     

Halogeno-Nitrosylkomplexe von Molybdän und Wolfram. Die Kristallstrukturen von [Na2(15-Krone-5)2(CH3CN)][MoCl4(NO)2] und [Na(15-Krone-5)]2[MoF4Cl(NO)]

Halogeno-Nitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of [Na₂(15-Crown-5)₂(CH₃CN)][MoCl₄(NO)₂] and [Na(15-Crown-5)]₂[MoF₄Cl(NO)] MoCl₂(NO)₂ and WCl₂(NO)₂, respectively, react with excess sodium fluoride in acetonitrile at room temperature and in the presence of 15-crown-5 to give crystalline mixtures, which consist of the title compounds, respectively of [Na(15-crown-5)]₂[WCl₄(NO)₂] and [Na(15-crown-5)]₂[WF₄Cl(NO)], and which can be separated by selection. The complexes are characterized by their i.r. spectra, the molybdenum compounds additionally by crystal structure determinations. [Na₂(15-crown-5)₂(CH₃CN)][MoCl₄(NO)₂]: Space group P2₁, Z = 2, 5415 independent unique reflexions, R = 0.039. Lattice dimensions at ?10°C: a = 984.3, b = 1231.1, c = 1483.0 pm, β = 105.67°. The compound consists of cations [Ne(l5-crown-5)(CH₃CN)]⁺, in which the sodium ion is surrounded by the five O-atoms of the crown ether and by the N-atom of the acetonitrile molecule, as well as of anions, which form an ion pair {Na(15-crown-5)[MoCl₄(NO)₂]}^?. In the in pairs the sodium ion is coordinated by the five oxygen atoms of the crown ether and by two chlorine atoms of the [MoCI₄(NO)₂]^2? unit. The nitrosyl ligands take the cis-position a t the molybdenum atom which is in a distorted octahedrally fashion. [Na(15-crown-5)]₂[MoF₄Cl(NO)]. Space group C2/c, Z = 4, 1933 independent unique reflexions, R = 0.078. Lattice dimensions at ?7O°C: D : 1.585.8, b = 1171.5, c = 1771.5 pm, β = 114.91°. The compound forms an ion triple, in which the sodium ions are linked to five oxygen atoms each of the crown ether molecules, and to two F-atoms of the [MoF₄Cl(NO)]^2? unit. The F-atom which is arranged in trans-position to the nitrosyl ligand coordinates with both sodium ions; thus an unusual T-shaped arrangement results for this F-atom. The sole terminal F-Atom and the Cl-atom are disordered in two positions.     

Kristallstrukturen und Schwingungsspektren von Tetrahalogenoacetylacetonatoosmaten(IV), [OsX4(acac)]−, X  Cl,Br, I

Crystal Structures and Vibrational Spectra of Tetrahalogenoacetylacetonatoosmates(IV), [OsX₄(acac)]^?, X ? Cl, Br, I By reaction of the hexahalogenoosmates(IV) with acetylacetone the tetrahalogenoacetylacetonatoosmates(IV) [OsX₄(acac)]^? (X = Cl, Br, I) are formed, which have been purified by chromatography and precipitated from aqueous solution as tetraphenylphosphonium (Ph₄P) or cesium salts. X-ray structure determinations on single crystals have been performed of (Ph₄P)[OsCl₄(acac)] ( 1 ) (triclinic, space group P1 , a = 9.9661(6), b = 11.208(2), c = 13.4943(7) Å, α = 101.130(9), β = 91.948(6), γ = 96.348(8)°, Z = 2), (Ph₄P)[OsBr₄(acac)] ( 2 ) (monoclinic, space group P2₁/n, a = 9.0251(8), b = 12.423(2), c = 27.834(2) Å, β = 94.259(7)°, Z = 4) and (Ph₄P)[OsI₄(acac)] ( 3 ) (monoclinic, space group P2₁/c, a = 18.294(3), b = 10.664(2), c = 18.333(3) Å, β = 117.68(2)°, Z = 4). Due to the increasing trans influence in the series O < Cl < Br < I the Os? O^. distances of O^.? Cl? X′ axes are lengthened and the OsO^. stretching vibrations are shifted to lower frequencies. The Os? X′ bond lenghts are shorter as compared with symmetrically coordinated X? Os? X axes.     

Darstellung von Nonahalogenodiplatinaten(IV), [Pt2X9]−, X  Cl,Br Spektroskopische Charakterisierung,Normalkoordinatenanalyse und Kristallstruktur von (PPN)[Pt2Br9]

Preparation of the Nonahalogenodiplatinates(IV), [Pt₂X₉]^?, X ? Cl, Br Spectroscopic Characterization, Normal Coordinate Analysis, and Crystal Structure of (PPN)[Pt₂Br₉] On heating the tetrabutylammonium salts (TBA)₂[PtX₆], with trifluoroacetic acid the nonahalogenodiplatinates(IV) (TBA)[Pt₂X₉], with X ? Cl, Br are formed. The X-ray structure determination on (PPN)[Pt₂Br₉] (orthorhombic, space group Pca2, Z = 4) shows for the anions pairs of face-sharing octahedra with nearly D_3h symmetry. The mean terminal and bridging Pt? Br bond lengths are determined to be 2.42 and 2.52 Å, respectively. The electrostatic interaction of the Pt atoms results in the Pt? Pt distance of 3.23 Å and an elongation as it has been forecasted by the MO scheme for d⁶ systems. Using the structural data a normal coordinate analysis based on a general valence force field for [Pt₂Br₉]^? has been performed, revealing a good agreement of the calculated frequencies with the bands observed in the IR and Raman spectra. The stronger bonding of the terminal as compared to the bridging ligands is shown by the valence force constants, f_a(Br₁) = 1,55 > f_d(Br_b) = 0,93 mdyn/ Å.     

Phosphanimin- und Phosphaniminato-Komplexe von Eisen. Die Kristallstrukturen von [FeCl3(Me3SiNPEt3)], [FeCl2(Me3SiNPEt3)]2, [FeCl2(NPEt3)]2 und [Fe(O2C?CH3)2(NPEt3)]2

Phosphanimine and Phosphoraneiminato Complexes of Iron. The Crystal Structures of [FeCl₃(Me₃SiNPEt₃)], [FeCl₂(Me₃SiNPEt₃)]₂, [FeCl₂(NPEt₃)]₂, and [Fe(O₂C? CH₃)₂(NPEt₃)]₂ The phosphanimine complexes [FeCl₃(Me₃SiNPEt₃)] (red-orange) and [FeCl₂(Me₃SiNPEt₃)]₂ (colourless) have been prepared by reactions of Me₃SiNPEt₃ with FeCl₃ and FeCl₂, respectively, in CH₂Cl₂ suspensions. Thermal decomposition of these donor-acceptor complexes in boiling toluene leads to the phosphoraneiminato complex [FeCl₂(NPEt₃)]₂ (black), whereas [Fe(O₂C? CH₃)₂(NPEt₃)]₂ (brown) is formed from iron(II) acetate and Me₃SiNPEt₃ in boiling acetonitrile. The complexes are characterized by IR spectroscopy and by crystal structure determinations. [FeCl₃(Me₃SiNPEt₃)] (1) : Space group P2₁/c, Z = 8, structure determination with 4 673 unique reflections, R = 0.033. Lattice dimensions at ?15°C: a = 1 607.8, b = 1 602.0, c = 1 417.2 pm, β = 106.56°. 1 forms monomeric molecules with tetrahedrally coordinated iron atoms. Bond lengths in average: Fe? N = 196.9 pm, Fe? Cl = 219.7 pm. [FeCl₂(Me₃SiNPEt₃)]₂ (2) : Space group P2₁/c, Z = 4, structure determination with 4 992 unique reflections, R = 0.048. Lattice dimensions at 20°C: a = 1 457.9, b = 1 685.4, c = 1 507.3 pm, β = 116.74°. 2 forms dimeric molecules, which are associated by chloro bridges. The iron atoms are tetrahedrally coordinated with trans positions of the phosphanimine ligands. Both lengths in average: Fe? N = 202.2 pm, Fe? Cl_terminal = 224.7 pm, Fe? Cl bridge = 241.0 pm. [FeCl₂(NPEt₃)]2 (3): Space group P2₁/n, Z = 2, structure determination with 2763 unique reflections, R = 0.039. Lattice dimensions at ?70°C: a = 799.1, b = 1009.0, c = 1441.9 pm, β = 93.45°. 3 forms centrosymmetric dimeric molecules, in which the tetrahedrally coordinated iron atoms are associated by the nitrogen atoms of the phosphoraneiminato ligands. Bond lengths in average: Fe? N = 191.4 pm, Fe? Cl = 222.7 pm. [Fe(O₂C? CH₃)₂(NPEt₃]2 (4): Space group P2₁/n, Z = 2, structure determination with 3005 observed unique reflections, R = 0.034. Lattice dimensions at -65°C: a = 886.4, b = 1444.6 pm, β = 90.60°. 4 forms centrosymmetric dimeric molecules, in which the octahedrally coordinated iron atoms are associated by the nitrogen atoms of the phosphoraneiminato ligands with bond lengths Fe? N of 191.9 and 195.0 pm. The acetate groups are coordinated in a chelating fashion.     

Darstellung,Kristallstruktur und spektroskopische Eigenschaften der Clusteranionen [(Mo6Br)X]2− mit Xa = F,Cl, Br,I

Synthesis, Crystal Structure and Spectroscopic Properties of the Cluster Anions [(Mo₆Br )X ]^2? with X^a = F, Cl, Br, I The tetrabutylammonium (TBA), tetraphenylphosphonium (TPP) and tetraphenylarsonium (TPAs) salts of the octa-μ₃-bromo-hexahalogeno-octahedro-hexamolybdate(2?) anions [(Mo₆Br)X]^2? (X^a = F, Cl, Br, I) are synthesized from solutions of the free acids H₂[(Mo₆Br)X] · 8 H₂O with X^a = Cl, Br, I. The crystal structures show systematic stretchings in the Mo? Mo bond length and a slight compression of the Brⁱ₈ cube in the F^a to I^a series. The cations do not change much. The i.r. and Raman spectra show at 10 K almost constant frequencies of the (Mo₆Brⁱ₈) cluster vibrations, whereas all modes with X^a ligand contribution are characteristically shifted. The most important bands are assigned by polarization measurements and the force constants are derived from normal coordinate analysis. The ⁹⁵Mo nmr signals are shifted to lower field with increasing electronegativity of the X^a ligands. The fluorine compound shows a sharp ¹⁹F nmr singlet at ?184.5 ppm.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Phosphaniminato-Komplexe des Titans. Synthese und Kristallstrukturen von CpTiCl2(NPMe3), [TiCl3(NPMe3)]2, [Ti2Cl5(NPMe2Ph)3] und [Ti3Cl6(NPMe3)5][BPh4]

Phosphoraneiminato Complexes of Titanium. Synthesis and Crystal Structures of CpTiCl₂(NPMe₃), [TiCl₃(NPMe₃)]₂, [Ti₂Cl₅(NPMe₂Ph)₃], and [Ti₃Cl₆(NPMe₃)₅][BPh₄] The title compounds are formed from Cp₂TiCl₂ and titanium tetrachloride, respectively, and the corresponding phosphane imino compounds Me₃SiNPMe₃ and Me₃SiNPMe₂Ph. The tetraphenyl borate salt yielded from the reaction of [Ti₃Cl₆(NPMe₃)₅]Cl with NaBPh₄. All compounds form yellow crystals which are sensitive to moisture. They were characterized by IR-spectroscopy and crystal structure analyses. CpTiCl₂(NPMe₃) ( 1 ): Space group Pbca, Z = 8, solution of the structure with 1632 observed independent reflections, R = 0.037. Lattice dimensions at 19°C: a = 1202.6, b = 1224.2, c = 1766.7 pm. The molecules of the compound are monomeric with the (NPMe₃)^? ligand in almost linear array (bond angle Ti? N? P 170.7°). [TiCl₃(NPMe₃)]₂ ( 2 ): Space group Pbca, Z = 8, structure solution with 698 observed independent reflections, R = 0.030. Lattice dimensions at ?60°C: a = 1140.5, b = 1112.2, c = 1589.4 pm. In 2 the titanium atoms, which occur in trigonal bipyramidal coordination, are linked by the N atoms of the (NPMe₃)^? groups to form a centrosymmetric dimer with Ti? N bond lengths of 184.3 and 208.2 pm. [Ti₂Cl₅(NPMe₂Ph)₃] · CH₂Cl₂ ( 3 ): Space group Pca2₁, Z = 4, structure solution with 8477 observed independent reflections, R = 0.051. The lattice dimensions at 20°C are: a = 1221.0; b = 1407.5, c = 2139.3 pm. 3 can be understood as a reaction product of TiCl₂(NPMe₂Ph)₂ and TiCl₃(NPMe₂Ph). In the resulting, heavily distorted Ti₂N₂-four-membered ring the Ti? N bond lenghts are 1804., 194.4, 199.2, and 234.6 pm. The longest Ti? N bond is in trans-position to the N atom of the terminal (NPMe₂Ph)- ligand, in which the Ti? N distance is 175.6 pm. .[Ti₃CL₆(NPMe₃)₅][BPh₄] (4): Space group P2₁/n, structure solution with 2846 observed independent reflections, R = 0.062. The lattice dimensions at 20°C are: a = 1495.2, b = 2335.4, c = 155,8 pm, β = 93.28°. In the cation of 4 the three titanium atoms along with three (NPMe₃)- groups with μ2- N functions and two (NPMe₃)- groups with μ3- N functions form a nation number 6 with two terminal chlorine atoms.     

Synthese und Kristallstrukturen der mehrkernigen Rhenium–Nitrido‐Komplexe [Re2N2Cl4(PMe2Ph)4(MeCN)] und [Re4N3Cl9(PMe2Ph)6]

Synthesis and Structures of the Multinuclear Rhenium Nitrido Complexes [Re₂N₂Cl₄(PMe₂Ph)₄(MeCN)] and [Re₄N₃Cl₉(PMe₂Ph)₆] The binuclear rhenium complex [Re₂N₂Cl₄(PMe₂Ph)₄(MeCN)] ( 1 ) is obtained as a byproduct of the synthesis of [(Me₂PhP)₃(MeCN)ClReNZrCl₅] from [ReNCl₂(PMe₂Ph)₃] and [ZrCl₄(MeCN)₂] in toluene. It crystallizes as 1 · 2 toluene in the monoclinic space group P2₁/n with a = 1517.0(3); b = 1847.7(2); c = 1952.4(6) pm; β = 106.44(1)° and Z = 4. The two Re atoms are connected by an asymmetric nitrido bridge Re≡N–Re with distances Re–N of 169.9(5) and 208.7(5) pm. In course of the reaction of [ReNCl₂(PMe₂Ph)₃] with [ZrCl₄(THF)₂] in CH₂Cl₂ hydrochloric acid is formed by acting of the Lewis acid on the solvent. HCl protonates and eliminates phosphine ligands of the educt [ReNCl₂(PMe₂Ph)₃] to form the phosphonium salt [PMe₂PhH]₂[ZrCl₆] ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 1536.9(3); b = 1148.8(1); c = 1402.2(3) pm, β = 100.70(2)° and Z = 4. The remaining fragments of the rhenium complex combine to yield the tetranuclear mixed valent complex [Re₄N₃Cl₉(PMe₂Ph)₆] ( 3 ), crystallizing as 3 · CH₂Cl₂ in the triclinic space group P 1 with a = 1312.9(19); b = 1661.4(2); 1897.1(2) pm; α = 78.62(1)°; β = 86.77(1)°; γ = 68.28(1)° and Z = 2. The four Re atoms occupy the corners of a tetrahedron. Its edges are formed by three nitrido and three chloro bridges. The asymmetric nitrido bridges Re≡N–Re are characterized by short distances in the range of 172(2) to 176(3) pm and long distances of 194(3) to 204(2) pm. The angles Re–N–Re are between 154(1) and 160(1)°.     

Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BBr2(NPMe3)]2, [B2Br3(NPiPr3)2]Br, [B2(NPEt3)4]Br2, [B2Br2(NPPh3)3]BBr4 und [{B2(NMe2)2}2(NPEt3)2]Cl2

Phosphoraneiminato Complexes of Boron. Syntheses and Crystal Structures of [BBr₂(NPMe₃)]₂, [B₂Br₃(NPⁱPr₃)₂]Br, [B₂(NPEt₃)₄]Br₂, [B₂Br₂(NPPh₃)₃]BBr₄ and [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl The bromoderivatives of the title compounds are prepared from the corresponding silylated phosphoraneimines Me₃SiNPR₃ and boron tribromide. The boron subcompound [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl₂ derives from Me₃SiNPEt₃ and B₂Cl₂(NMe₂)₂. All complexes are characterized by NMR and IR spectroscopy as well as by crystal structure determinations. [BBr₂(NPMe₃)]₂ (1): Space group P2₁/n, Z = 2, R = 0.031. Lattice dimensions at ?50°C: a = 723.8, b = 894.2, c = 1305.4 pm, β = 92.35°. 1 forms centrosymmetric molecules in which the boron atoms are linked via μ₂-N bridges of the NPMe₃^? groups of from B₂N₂ four-membered rings with B? N distances of 149.9 and 150.9 pm. B₂Br₃(NPⁱPr₃)₂]Br (2): Space group P2₁, Z = 2, R = 0.059. Lattice dimensions at ?80°C: a = 817.6, b = 2198.7, c = 851.5 pm, β = 115.09°. In the cations of 2 the boron atoms are lined via the μ₂-N atoms of the NPⁱPr₃^? groups to form planar, asymmetric B₂N₂ four-membered rings with B? N distances of 143 and 156 pm. [B₂(NPEt₃)₄[Br₂·4CH₂Cl₂ (3): Space group C2/c, Z = 4, R = 0.042. Lattice dimensions at ?50°C: a = 1946.1, b = 1180.3, c = 2311.3 pm, β = 101.02°. The structure contains centrosymmetric dications in which both the boron atoms are lined by the N atoms of two of the NPEt₃^? groups to form a B₂N₂ four-membered ring with B? N distances of 149.6 pm. The remaining two NPEt₃^? groups are terminally bonded with very short B? N distances of 133.5 pm. B₂Br₂(NPPh₃)₃]BBr₄ (4): Space group P1 , Z = 2, R = 0.065. Lattice dimension at ?50°C: a = 1025.7, b = 1496.1, c = 1807.0 pm, α = 85.09°, β = 82.90°, γ = 82.72°. In the cation the boron atoms are lined via the μ₂-N atoms of two of the NPPh₃^? groups to form a nearly planer B₂N₂ four-membered ring with B? N distances of 149.3-153.1 pm. The third NPPh₃³ group is terminally connected with teh sp² hybridized boron atom and with a B? N distance of 134.1 pm along with an almost linear BNP bond angle of 173.6°. [{B₂(NMe₂)₂}₂(NPEt₂)₂]Cl₂ · 3CH₂Cl₂ (5): Space group C2/c, Z = 4, R = 0.098. Lattice dimensions at ?70°C: a = 1557.9, b = 1294.7, c = 2122.9 pm, β = 96.08°. The structure of 4 contains centrosymmetric dications in which two by two B-B dumb-bells are linked via the μ₂-N atoms of the two NEPt₃^? groups to form B₄N₂ six-membered rings with B? N distances of 150 and 156 pm and B-B distances of 173 pm. The B? N distances of the terminally bonded NMe₂^? groups correspond to 138 pm double bonds.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl,S2CH)

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], [Ru₂(CO)₄(μ‐X)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (X = Cl, S₂CH) [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS₂ into the Ru₂(μ‐H) bridge the dithioformato complex [Ru₂(CO)₄(μ‐S₂CH)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF₄] to the complex salt [Ru₂(CO)₄(μ‐NO)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)][BF₄] ( 4 ), and reaction of 1 with CCl₄ or CHCl₃ affords spontaneously [Ru₂(CO)₄(μ‐Cl)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.