Heterometallatom-Koordinationsverbindungen Re2(μ-PPh2)2[mer-(CO)3]2-trans-[InX2(H2O)]2 und neue halogenhaltige drei- und vierkernige Rheniumcluster aus Reaktionen zwischen Re2[μ-PPh2)2(CO)8] und InX3 (X = Cl,Br, I)

Heterometallic Coordination Compounds Re₂(μ-PPh₂)₂[mer-(CO)₃]₂-trans-[InX₂(H₂O)]₂ and New Halogene Containing Three- and Four-Nuclear Rhenium Clusters from Reactions between Re₂(μ-PPh₂)₂(CO)₈ and InX₃ (X = Cl, Br, I) In sealed glass tubes equimolar amounts of Re₂(μ-PPh₂)₂(CO)₈ and InX₃ (X = Cl, Br, I) were reacted in the presence of xylene at 220°C to two types of products. The first type comprised the heterometallic coordination compounds Re₂(μ-PPh₂)₂(CO)₆[InX₂(H₂O)]₂ (X = Cl, Br, I) (yield 60%), and the second halogene containing rhenium complexes Re₃(μ₃-H)(μ₃-X)(μ-PPh₂)₃(CO)₆ (unsaturated three-membered metal ring with 46 VE) and Re₄(μ-H)(μ-X)(μ-PPh₂)₄(μ₄-PPh)(CO)₈ and additionally those substances as cis-IRe(CO)₄(PPh₂H), Re₂(μ-PPh₂)(μ-X)(CO)₈ (X = Cl, Br), Re₂(μ-I)₂[μ-(PPh₂)₂O](CO)₆ and Re₄(μ-Cl)₂(μ-PPh₂)₄(μ₄-PPh)(CO)₈ (four-membered metal ring with 66 VE with three Re? Re bonds) which have been observed in one or two of the three reaction systems. A proposal of the reaction course is discussed. The single X-ray analysis of Re₂(μ-PPh₂)₂[mer(CO)₃]₂-trans[InI₂(H₂O)]₂ · 2 Me₂CO shows for the two fold phosphido bridged dirhenium molecular fragment with 34 VE a Re? Re bond of 294.6(1) pm. From two possible transpositions of both In? Re bond vectors, the one found advantageously has sterical reasons. The average In? Re single bond length is 271.1(1) pm. The corresponding determination of the unsaturated three-membered ring compound Re₃(μ₃-H) (μ₃-Cl)(μ-PPh₂)₃(CO)₆ showed three Re? Re bond lenghts of comparable size, of which the mean value of 281.9(1) pm was significantly shortened by π electron delocalization effect compared to that of a saturated phosphido bridged three-membered rhenium ring compound. As it was recognized by further comparison, the structural data of the common molecular fragments in the three examined three-membered rhenium ring clusters (X = Cl, Br, I) are not dependent on the different kind of halogeno ligand atoms. Finally, the crystal structure determination of the substance Re₄(μ-H)(μ-Br)(μ-PPh₂)₄(μ₄-PPh)(CO)₈ shows the presence of square-pyramidal Re₄(μ₄-P) atomic arrangement, of which the planar basic plane has a sequence of up- and downwards orientated four diphenylphosphido bridging groups. The four measured Re? Re single bond lengths (mean value 302.7(3) pm change with the different kind of bridging atoms. The structural features observed are compared with those of a corresponding iodine derivative.     

Re4(CO)12[μ3-InRe(CO)5]4 und Re2(CO)8[μ-InRe(CO)5]2-cluster aus dem reaktionssystem In/Re2(CO)10 in xylol

The thermally stable solids Re₂(CO)₈[μ-InRe(CO)₅]₂ and Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ could be obtained by treatment of In with Re₂(CO)₁₀ in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re₂(CO)₈[μ-InRe(CO)₅]₂, Re₄(CO)₁₂[μ₃_InRe(CO)₅]₄ shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re₄(CO)₁₂-[μ₃-InRe(CO)₅]₄ dissolves monomerically in acetone, where as Re₂(CO)₈[μ-InRe(CO)₅]₂ dissociates yielding Re(CO)₅^? anions. Single-crystal X-ray analyses of Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ establish the metal skeleton. The central molecular fragment Re₄(CO)₁₂ contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ₃-InRe(CO)₅ group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re₄ tetrahedron and the metal skeleton was realized for the first time. By treating Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ with Br₂ the existence of Re(CO)₅ ligands could be proved by isolating BrRe(CO)₅.     

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}.     

Heteronukleare Metallatomcluster der Typen X4−n[SnM(CO)4P(C6H5)3]n und M2(CO)8 [μ-Sn(X)M (CO)4P(C6H5)3]2 aus Umsetzungen von SnX2 mit M2(CO)8[P(C6H5)3]2 (X = Halogen; M = Mn,Re; n = 2, 3)

Heteronuclear Metal Atom Clusters of the Types X_4?n[SnM(CO)₄P(C₆H₅)₃]_n and M₂(CO)₈[μ-Sn(X)M(CO)₄P(C₆H₅)₃]₂ by Reaction of SnX₂ with M₂(CO)₈[P(C₆H₅)₃]₂ (X = Halogene; M = Mn, Re; n = 2, 3) The compounds of the both types X_4?n[SnM(CO)₄P(C₆H₅)₃]_n (n = 3; M = Mn; X = F, Cl, Br, I. n = 2: M = Mn, Re; X = Cl, Br, I) and M₂(CO)₈[μ-Sn(X)M(CO)₄P(C₆H₅)₃]₂ (M = Mn; X = Cl, I. M = Re; X = Cl, Br, I) are prepared by reaction of SnX₂ with M₂(CO)₈[P(C₆H₅)₃]₂ (M = Mn, Re). Their IR frequencies are assigned. In Re₂(CO)₈[μ-Sn(Cl)Re(CO)₄P(C₆H₅)₃]₂ the central molecule fragment contains a planar Re₂Sn₂ rhombus with a transannular Re? Re bond of 316.0(2) pm. Each of the Sn^IV atoms is connected with the terminal ligands Cl and Re(CO)₄P(C₆H₅)₃. These ligands are in transposition with respect to the Re₂Sn₂ ring. The mean values for the remaining bond distances (pm) are: Sn? Re = 274.0(3); Sn? Cl = 243(1), Re? C = 176(5), Re? P = 242.4(9), C? O = 123(5). The factors with an influence on the geometrical shape of such M₂Sn₂ rings (M = transition metal) are discussed.     

Zur Nucleophilie des sterisch anspruchsvollen Basenanions von Lithiumdiisopropylamid beim Protonenersatz gegen das isolobale AuPPh3-Kation in [(μ-H)(μ-PPh2) (CO)8Re2]

Nucleophilic Property of the Bulk Anion of the Base Lithium diisopropylamide at the Proton Exchange vs. the Isolobal AuPPh₃ Cation in [(μ-H) (μ-PPh₂) (CO)₈Re₂] The proton exchange in the starting material [(μ-H)(μ-PPh₂)(CO)₈Re₂] vs. the isolobal [AuPPh₃]⁺ cation when reacted with the steric expansive base LDA depending on reaction temperature leads to the three-membered metal ring substance [(μ-PPh₂)(CO)₈Re₂(AuPPh₃)] or the metallatetrahedron complex [(μ-C-(N i-Prop₂)O)(μ-PPh₂)(CO)₆Re₂(AuPPh₃)₂]. The tetrahedral cluster compound obtained through the nucleophilic property of LDA shows by means of cyclic voltammetry a reversible and a irreversible one-electron transfer redox step. The single crystal X-ray analysis of the compound with a tetrahedral Au₂Re₂ core gives following values of metal-metal bond lengths: Re? Re 312.2(2) pm, Au? Au 270.9(2) pm, and Au? Re 297.7(2) pm. The acyl diisopropylamido groups bridging the Re? Re bond is planar.     

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.     

[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O,ein gemischtes Halogenid-Hydrat mit anionischen Dimeren {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2−

[Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2? [Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl₃ and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; V_m = 573.9(4) cm³mol^?1; R = 0.060; R_w = 0.038) is the connection of two anions [Re₃(μ-Cl)₃Br₇(H₂O)₂]^? via a water molecule to dimers, {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2?. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb⁺ cations and crystal water.     

Halogenverbrückte Heterometallatomcluster der drei Typen Re2(CO)4L2(μ-X)2(μ-Y) (L = (C6H5)3P; X = Br,I; Y = GaRe(CO)4ax-L), Re2(CO)6L2(μ-X)(μ-GaX2) (X = I) und Re3(CO)9L3(μ-X)3(μ-Y) (X = Cl)

Halogeno-Bridged Heteronuclear Metal Atom Clusters of the Three Types Re₂(CO)₄L₂(μ-X)₂(μ-Y) (L = (C₆H₅)₃P; X = Br, I; Y = GaRe(CO)₄ax-L), Re₂(CO)₆L₂(μ-X) (μ-GaX₂) (X = I), and Re₃(CO)₉L₃ (μ-X)₃(μ₃-Y) (X = Cl) The title compounds of the both types Re₂(CO)₄L(μ-X)₂(μ-Y) [L = (C₆H₅)₃P; X = Br, I; Y = GaRe(CO)₄ax-L] and Re₃(CO)₉L₃(μ-X)₃ (μ₃-Y) (X = Cl) were prepared by the reaction of GaX₃ (X = Cl, Br, I) and Re₂(CO)₈(ax-L)₂ in boiling mesitylene solution. The obtained substance Re₂(CO)₄L₂(μ-I)₂(μ-Y) and carbon monoxide gave the compound of the third type Re₂(CO)₆L₂(μ-I)(μ- GaI₂). The last-named single iodo-bridged dirhenium cluster could be therefore a precursor complex of the double iodo-bridged compound. The four diamagnetic substances were characterized by ³¹P n.m.r. spectroscopy and their molecular structures were acertained by X-ray measurements. The result of the single crystal X-ray analysis of Re₂(CO)₄L₂(μ-Br)₂ [μ-GaRe(CO)₄ax-L], a bridged coordination octahedron pair with a common face, and that of the edge-bridged pair Re₂(CO)₆L₂(μ-I)(μ-GaI₂) each possessing a Re? Re bond are especially treated in the present work.     

Darstellung und Strukturen von (Et4N)2[Re(CO)3(NCS)3] und (Et4N)[Re(CO)2Br4]

Syntheses and Structures of (Et₄N)₂[Re(CO)₃(NCS)₃] and (Et₄N)[Re(CO)₂Br₄] Rhenium(I) and rhenium(III) carbonyl complexes can easily be prepared by ligand exchange reactions starting from (Et₄N)₂[Re(CO)₃Br₃]. Using nonoxidizing reagents the facial Re^I(CO)₃ unit remains and only the bromo ligands are exchanged. Following this procedure, (Et₄N)₂[Re(CO)₃(NCS)₃] can be obtained in high yield and purity using trimethylsilylisothiocyanate. The compound crystallizes in the monoclinic space group P2₁/n, a = 18.442(5), b = 17.724(3), c = 18.668(5) Å, β = 92.54(1)°, Z = 8. The NCS^? ligands are coordinated via nitrogen. The reaction of [Re(CO)₃Br₃]^2? with Br₂ yields the rhenium(III) anion [Re(CO)₂Br₄]^?. The tetraethylammonium salt of this complex crystallizes in the noncentrosymmetric, orthorhombic space group Cmc2₁, a = 8.311(1), b = 25.480(6), c = 8.624(1) Å, Z = 4. The carbonyl ligands are positioned in a cis arrangement. Their strong trans influence causes a lengthening of the Re? Br bond distances by at least 0.05 Å.     

Darstellung von μ-Hydrido-μ-diphenylphosphido-bis(tetracarbonylrhenium) · 1/2 Xylol und Molekülstruktur des Derivates Re2(CO)6(PPh3)2(μ-H)(μ-PPh2) (Ph = C6H5)

Preparation of μ-Hydrido-μ-diphenylphosphido-bis(tetracarbonylrhenium) · 1/2 Xylene and Molecular Structure of the Derivative Re₂(CO)₆(PPh₃)₂(μ-H)(μ-PPh₂) (Ph = C₆H₅) The reaction of dirhenium decacarbonyl with diphenylphosphine in xylene solution gave at 190–200°C in a glas tube crystals of Re₂(CO)₈(μ-H)(μ-PPh₂) · 1/2 C₈H₁₀. The obtained adduct was reacted in the same solvent with an excess of triphenylphosphine to the derivative Re₂(CO)₆(PPh₃)₂(μ-H)(μ-PPh₂). Both diamagnetic dirhenium compounds with μ-H atom and μ-PPh₂ group were characterized by ¹H and ³¹P spectroscopic measurements. The molecular structure of the derivative was acertained by a single crystal X-ray analysis. Its result showed a three-membered Re₂(μ-P) ring as central molecular fragment. At these Re central atoms were attached two PPh₃ ligands in an unprefered cis-arrangement due to sterical reasons. A thermodynamic transinfluence of the (μ-P)? Re bond favoured the found positions of the PPh₃ ligands.     

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)°.     

Metallorganische Verbindungen der Lanthanoide. LIII [1].(C5H5Gd)5(μ2-OCH3)4(μ3-OCH3)4(μ5-O) und [Na2(tC4H9OGd)4(μ3-OtC4H9)8(μ6-O)], zwei neue Alkoxigadoliniumcluster mit interstitiellem Sauerstoff

Organometallic Compounds of the Lanthanides. LIII. (C₅H₅Gd)₅(μ₂-OCH₃)₄(μ₃-OCH₃)₄ (μ₅-O) and [Na₂(^tC₄H₉OGd)₄(μ₃-O^tC₄H₉)₈(μ₆-O)], two New Alkoxi Gadolinium Clusters with Interstitial Oxygen Gadolinium trichloride reacts in tetrahydrofurane with cyclopentadienyl sodium and two equivalents of sodium methoxide with formation of (C₅H₅Gd)₅(μ₂-OCH₃)₄(μ₃-OCH₃)₄(μ₅-O) ( 1 ), and with potassium tert-butoxide with formation of [Na₂(^tC₄H₉OGd)₄(μ₃-O^tC₄H₉)₈(μ₆-O)] ( 2 ). The X-ray structure of 1 shows a tetragonal pyramide build up by five gadolinium atoms, containing an oxygen atom in the center of the base and eight bridging methoxo groups. The structure of 2 consists of an oxygen centered octahedron build up by two sodium and four gadolinium atoms, connected by eight bridging tert-butoxy groups and four terminal butoxides. The monoclinic crystals of 1 , space group I2/a have the following crystallographic data: a = 2 276.9(5) pm, b = 2 063.1(6) pm, c = 3 152.2(3) pm, β = 90.7(1)°, Z = 12, D_calcd 1.85 g · cm^?3, R = 0.0519. 2 crystallizes tetragonal, space group I4/mmm with a = 1 728.5(4) pm, b = 1 031.0(3) pm, Z = 2, D_calcd 1.69 g · cm^?3, R = 0.0682.     

Zur Selektivität des isolobalen Protonenaustausches im Hydrido/Phosphidoverbrückten Dirhenium-Komplex Re2(μ-H)(μ-PCyH)(CO)8

On the Selectivity of the Isolobal Proton Exchange in the Hydrido/Phsophido Bridged Dirhenium Complex Re₂(μ-H)(μ-PCyH)(CO)₈ H₂PCy and Re₂(CO)₁₀ in Xylene were heated in a sealed glass tube at 170°C for 18 h to afford Re₂(μ-H)(μ-PCyH)(CO)₈ in a yield of 30% and the cis/trans isomer pair Re₂(μ-PCyH)₂(CO)₈ in yields of 27% (trans) and 21% (cis). The isomer trans Re₂(μ-PCyH)₂(CO)₈ could be partially converted to the cis isomer by deprotonation with the non nucleophilic base DBU or by heating in xylene solution. The complex Re₂(μ-H)(μ-PCyH)(CO)₈ which is bifunctional relative to a proton abstraction was treated with equimolar amounts of DBU to generate [Re₂(μ-H)(μ-PCy)(CO)₈]^? under release of the more acidic proton from the PH group. Subsequently, this anion undergoes an isomerization to the thermodynamically more stable [Re₂(μ-PCyH)(CO)₈]^? by proton transfer. Such knowledge about the isomeric anions enabled us to synthesize selectively the monoaurated isomers Re₂(μ-AuPPh₃)(μ-PCyH)(CO)₈ and Re₂(μ-H)(μ₃-PCy(AuPPh₃))(CO)₈ in good yields by reaction with equimolar amounts of the electrophil ClAuPPh₃. In the presence of excess DBU and a twofold amount of ClAuPPh₃ the complex Re₂(μ-H)(μ-PCyH) · (CO)₈ formed the diaurated complex Re₂(μ-AuPPh₃)(μ₃-PCy(AuPPh₃))(CO)₈ (91%). Compared to the corresponding known dimanganese-gold isomers, each of the analogous dirhenium-gold complexes obtained showed no tendency for an isomerization process. Finally, the single crystal X-ray analyses of the three dirhenium-gold complexes led to the subsequent Re? Re bond lengths: 313,6(1) pm in Re₂(μ-H)(μ₃-PCy(AuPPh₃))(CO)₈, 316,8(2) pm in Re₂(μ-AuPPh₃)(μ₃PCy(AuPPh₃))(CO)₈ and 326,1(2) pm in Re₂(μ-AuPPh₃)(μ-PCyH)(CO)₈.     

Synthese und Struktur von (PPh4)3[Re2NCl10]

Synthesis and Crystal Structure of (PPh₄)₃[Re₂NCl₁₀] The rhenium(V) nitrido complex (PPh₄)₃[Re₂NCl₁₀] ( 1 ) is obtained from the reaction of (PPh₄)[ReNCl₄] with 1, 3‐dioxan‐(2‐ylmethyl)diphenyl phosphine in CH₂Cl₂/CH₃CN in form of orange red crystals with the composition 1 ·2CH₂Cl₂ crystallizing in the triclinic space group P1¯ with a = 1210.7(2), b = 1232.5(1), c = 2756.3(5) pm, α = 99.68(1)°, β = 100.24(1)°, γ = 98.59(1)° and Z = 2. The crystal structure contains two symmetry independent, centrosymmetrical complex anions [Re₂NCl₁₀]^3‐ with a symmetrical nitrido bridge Re=N=Re and distances Re(1) ‐ N(1) = 181.34(5) and Re(2) ‐ N(2) = 181.51(4) pm.     

Darstellung und Kristallstrukturen von (Ph3PNPPh3)2[Re2Br10] und (Ph4P)[Re2Br9]

Synthesis and Crystal Structures of (Ph₃PNPPh₃)₂[Re₂Br₁₀] and (Ph₄P)[Re₂Br₉] Depending on the molar ratio by reaction of [n-Bu₄N]₂[ReBr₆] with the Lewis acid BBr₃ in dichloromethane the bioctahedral complexes [n-Bu₄N]₂[Re₂Br₁₀] and [n-Bu₄N][Re₂Br₉] are formed. The X-ray structure determination on (Ph₃PNPPh₃)₂[Re₂Br₁₀] (monoclinic, space group C 2/c, a = 20.007(4), b = 15.456(5), c = 24.695(4) Å, β = 107.53(2)°, Z = 4) reveals a centrosymmetric edge-sharing complex anion with approximate D_2h symmetry and mean terminal and bridging Re–Br bond lengths of 2.453 (equatorial), 2.482 (axial) and 2.591 Å, respectively, and a Re–Re distance of 3.880 Å. (Ph₄P)[Re₂Br₉] (triclinic, space group P 1, a = 11.062(2), b = 12.430(3), c = 13.163(5) Å, α = 72.94(2), β = 68.47(2), γ = 82.09(2)°, Z = 2) contains a confacial bioctahedral anion with nearly D_3h symmetry and mean terminal and bridging Re–Br distances of 2.460 and 2.536 Å, respectively, and a Re–Re distance of 2.780 Å.     

Neue Phosphor-verbrückte Übergangsmetallcarbonyl-Komplexe Die Kristallstrukturen von [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6] und [Ni4(CO)10(PiPr)6]

New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re₂(CO)₇(P^tBu)₃], [Co₄(CO)₁₀(P^tBu)₂], [Ir₄(CO)₆(P^tBu)₆], and [Ni₄(CO)₁₀(PⁱPr)₆], (P^tBu)₃ reacts with [Mn₂(CO)₁₀], [Re₂(CO)₁₀], [Co₂(CO)₈] and [Ir₄(CO)₁₂] to form the multinuclear complexes [M₂(CO)₇(P^tBu)₃] (M = Re ( 1 ), Mn ( 5 )), [Co₄(CO)₁₀(P^tBu)₂] ( 2 ) and [Ir₄(CO)₆(P^tBu)₆] ( 3 ). The reaction of (PⁱPr)₃ with [Ni(CO)₄] leads to the tetranuclear cluster [Ni₄(CO)₁₀(PⁱPr)₆] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P2₁/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).     

Nitrosylbromokomplexe des Rheniums: Re(NO)2Br3 und [Re(NO)2Br4]⊖; die Kristallstruktur von PPh4[Re(NO)2Br4] · 2 CCl4

Nitrosyl Bromo Complexes of Rhenium: Re(NO)₂Br₃ and [Re(NO)₂Br₄]^?; Crystal Structure of PPh₄[Re(NO)₂Br₄] · 2 CCl₄ PPh₄[Re(NO)₂Br₄] is prepared in the form of dark red-brown powder by the reaction of PPh₄[Re(NO)₂Cl₄] with excess boron tribromide. From a solution of CH₂Br₂ and CCl₄ it crystallizes with two moles CCl₄, one of which splits off easily in vacuo. The reaction of aluminum tribromide in CH₂Br₂ solution leads to a slightly soluble red-brown Re(NO)₂Br₃ powder. The i.r. spectra indicate cis positions of the covalently bound NO ligands in both complexes. Re(NO)₂Br₃ is dimeric via bromo bridges. The crystal structure determination of PPh₄[Re(NO)₂Br₄] · 2 CCl₄ was solved by X-ray diffraction methods at ? 115°C. The complex crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell (4434 independent reflexions, R = 0.085). The unit cell dimensions are a = 1 092.3 pm, b = 2088.0 pm, c = 1 657.6 pm, β = 96.10°. The structure consists of P(C₆H₅)₄^? cations, [Re(NO)₂Br₄]^? anions and intercalated CCl₄ molecules. In the anion the NO groups are covalently bound to the Re atom like \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {{\rm RE}}\limits^ \ominus = \mathop {\rm N}\limits^ \oplus = {\rm O} $\end{document} and they are arranged in cis position to one another.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2NbCl4 und [Re3N3Cl5(PMe2Ph)6][NbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂NbCl₄ and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] The reaction of ReNCl₂(PMe₂Ph)₃ with NbCl₅ in toluene yields the trinuclear complexes [(Me₂PhP)₃Cl₂ReN]₂‐ NbCl₄ (1) and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] ( 2 ). 1 forms triclinic crystals with the composition 1 · 2 C₇H₈ (P 1, a = 1074.5(1), b = 1289.1(2), c = 1299.3(2) pm, α = 85.25(2)°, β = 81.04(2)°, γ = 86.02(1)°, Z = 1). In the centrosymmetric compound 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit NbCl₄ to form an almost linear arrangement Re≡N–Nb–N≡Re. The length of the Re–N triple bonds is 172,2 pm, and the Nb–N distances of 216.0 pm correspond to coordinative single bonds. 2 forms orthorhombic crystals with the space group P2₁2₁2₁ and a = 1286.0(1), b = 2109.2(4), c = 2436.2(3) pm, Z = 4. The three Re atoms are located at the corners of a triangle. They are connected by two asymmetric nitrido bridges and two asymmetric chloro bridges. The weakly bent nitrido bridges (Re–N–Re = 152° and 157°) are characterized by Re–N distances of 169 und 207 pm as well as 171 and 207 pm. Re1, in addition, binds a terminal nitrido ligand with Re1–N1 = 166 pm.     

New compounds in the cesium sulfobromide rhenium octahedral cluster chemistry: syntheses and crystal structures of Cs4Re6S8Br6 and Cs2Re6S8Br4

The exploration of the CsReSBr system, in order to identify new phases based on octahedral cluster anions, has produced single crystals of Cs₄Re₆S₈Br₆ (1) (trigonal, space group P-6c2, a=9.7825 (3) Å, c=18.7843 (5) Å, V=1556.77 (1) ų, Z=2, density=5.09 g cm⁻³, μ=36.07 mm⁻¹) and Cs₂Re₆S₈Br₄ (2) (monoclinic, space group P2₁/n, a=6.3664 (1) Å, b=18.4483 (4) Å, c=9.3094 (2) Å, β=104.2618 (8)°, V=1059.69 (4) ų, Z=2, density=6.14 g cm⁻³, μ=45.83 mm⁻¹). These two compounds have been obtained by high-temperature solid state route. Their structures have been solved and refined from single crystal X-ray diffraction data. The structure of Cs₄Re₆S₈Br₆ presents isolated anionic cluster units inscribed in a (Cs⁺)₁₂ cuboctahedron and the one of Cs₂Re₆S₈Br₄ exhibits ReS^i-a,a-iRe inter-unit bridges. The framework of the latter presents then a strongly 1-D character.     

Disulfidoverbrückte Halogenokomplexe von Molybdän(V) Kristallstrukturen von (PPh3Me)2[Cl4Mo(μ-S2)2MoCl4] · 2 CH2Cl2 und (PPh4)2[Br4Mo(μ-S2)2MoBr4] · 3 CH2Br2

Disulfido-Bridged Halo Complexes of Molybdenum (V). Crystal Sructures of (PPh₃Me)₂ [Cl₄Mo (μ-S₂)₂MoCl₄]. 2 CH₂Cl₂ and (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄]. 3CH₂Br₂ . Mo(S₂)Cl₃ is prepared by an improved method; the i.r. spectrum is reported. In dichloro methane solution it reacts with (PPh₃Me)Cl forming the complex (PPh₃Me)₂[Cl₄Mo(μ-S₂)₂MoCl₄] · 2 CH₂Cl₂. The bromo complex (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄] · 3 CH₂Br₂ is obtained by reaction of MoBr₄ with S₇NH and subsequent treatment of the reaction mixture with PPh₄Br in CH₂Br₂ solution. Both complexes are characterized by i.r. spectra and structural analyses by X-ray methods. (PPh₃Me)₂[Cl₄Mo(μ-S₂)₂MoCl₄] · 2 CH₂Cl₂ crystallizes monoclinic in the space group P2₁/c with two formula units per unit cell (5268 observed independent reflexions, R = 4.0%). The lattice dimensions are: a = 1097 pm, b = 1510 pm, c = 1591 pm, β = 104.4°. (PPh₄)₂[Br₄Mo(μ-S₂)₂MoBr₄] · 3 CH₂Br₂ crystallizes triclinic in the space group P&1macr; with two formula units per unit cell and the lattice constants a = 1328 pm, b = 1573 pm, c = 1719 pm, α = 95.8°, β = 96.3°, γ = 74.1°. Both compounds are of ionical structure with PPh₃Me^⊕ and PPh₄^⊕ cations, respectively, and anions [X₄MO(μ-S₂)₂MoX₄]^2? very similar to each other. The molybdenum atoms are bridged by two disulfido ligands and are bonded directly with a bond length of 286 pm. The terminal halogen atoms add up to coordination number nine at the molybdenum.