Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)3L(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (L = CO,PnBu3)

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru₂(CO)₃L(μ‐η¹ : η²‐C≡CPh)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (L = CO, PⁿBu₃) [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 1 ) reacts with several phosphines (L) in refluxing toluene under substitution of one carbonyl ligand and yields the compounds [Ru₂(CO)₃L(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] (L = PⁿBu₃, 2 a ; L = PCy₂H, 2 b ; L = dppm‐P, 2 c ; dppm = Ph₂PCH₂PPh₂). The reactivity of 1 as well as the activated complexes 2 a – c towards phenylethyne was studied. Thus 1 , 2 a and 2 b , respectively, react with PhC≡CH in refluxing toluene with elimination of dihydrogen to the acetylide‐bridged complexes [Ru₂(CO)₄(μ‐η¹ : η²‐C≡CPh)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ) and [Ru₂(CO)₃L(μ‐η¹ : η²‐C≡CPh)(μ‐P^tBu₂)(μ‐dppm)] ( 4 a and 4 b ). The molecular structures of 3 and 4 a were determined by crystal structure analyses.     

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.     

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.     

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.     

Binuclear CpV,Cp*V,and Cp*Ta Complexes containing Organochalcogenolato Bridges, μ‐ER (E = Sulfur,Selenium, Tellurium; R = Methyl,Phenyl, and Ferrocenyl)

Photolysis of the halfsandwich tetracarbonylmetal complexes CpV(CO)₄, Cp*V(CO)₄ and Cp*Ta(CO)₄ in solution in the presence of di(organyl)dichalcogenides E₂R₂ (E = S, Se, Te; R = Me, Ph, Fc) leads to diamagnetic doubly organochalcogenolato‐bridged compounds, [Cp⁽⁾M(CO)₂(μ‐ER)]₂. According to the X‐ray structure determinations carried out for [CpV(CO)₂(μ‐TeMe)]₂, [Cp*V(CO)₂(μ‐TePh)]₂ and [Cp*Ta(CO)₂(μ‐SPh)]₂, the molecular framework consists of a folded M₂(μ‐ER)₂ ring with the cyclopentadienyl ligands in cis‐configuration and the organyl substituents R in a syn‐equatorial arrangement, thus forming a bowl‐shaped molecule with the four terminal CO ligands protruding into the inner sphere. The M…M distances (in the range between 305 and 330 pm) are not considered to indicate direct bonding interactions. The vanadium complexes [Cp⁽⁾V(CO)₂(μ‐ER)]₂ are completely decarbonylated in the presence of an excess of E₂R₂ in boiling toluene, and in many cases the paramagnetic quadruply‐bridged products, [CpV(μ‐ER)₂]₂, can be isolated.     

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.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)n(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (n = 4; 5) und [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru₂(CO)_n(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (n = 4; 5) and [Ru₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] The reaction of [Ru₂(μ‐CO)(CO)₅(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 2 ) with dppm yields the dinuclear species [Ru₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ) (dppm = Ph₂PCH₂PPh₂). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ). 4 is also obtainable by an one‐pot synthesis from [Ru₃(CO)₁₂], an excess of ^tBu₂PH and stoichiometric amounts of dppm via the formation of [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)₂] ( 1 ). 4 exhibits a Ru–Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ). The molecular structures of 3 , 4 and 5 were determined by X‐ray crystal structure analyses.     

Zweikernkomplexe des Typs Mn2(CO)8E(CF3)2E′R (E = P,As; E′ = S,Se, Te): Darstellung und Struktur

Perfluoromethyl Element Ligands. XLII Binuclear Complexes of the Type Mn₂(CO)₈E(CF₃)₂E′R (E = P, As; E′ = S, Se, Te): Synthesis and Structure Complexes of the type Mn₂(CO)₈E(CF₃)₂E′R, in which the groups E(CF₃)₂ and E′R act as bridging ligands, are prepared either by direct reactions of Mn₂(CO)₁₀ with (F₃C)₂EE′R (E = P, As; E′ = S, Se, Te) or by substitution of the iodine bridge in the representatives Mn₂(CO)₈ E(CF₃)₂I (E = P, As) with mercury compounds Hg(E′R)₂. As a rule the binuclear systems contain four‐membered heterocycles (Mn₂EE′). However, the reactions of Mn₂(CO)₁₀ with (F₃C)₂PE′P(CF₃)₂ (E′ = S, Se) yield five‐membered rings [Mn₂P(E′P)]. The compounds have been characterized by spectroscopic (NMR, IR, MS), analytic (C, H) and X‐ray diffraction investigations. The pyramidal Mn₂E′R fragment shows dynamic behaviour in solution via inversion between two identical structures.     

{Ph2(Carb)P}MCl3 (M = Pd,Pt; Carb = 2,3-dihydro-1,3-diisopropyl-4,5dimethylimidazol-2-ylidene) – a Novel Cationic Phosphane Ligand [1]

The phosphane ligand [Ph₂(Carb)P]⁺ forms neutral complexes {Ph₂(Carb)P}MCl₃ (Carb = 2,3-dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; M = Pd, Pt) through the reaction of it's chloride salt with (PhCN)₂MCl₂; the triarylphosphane type properties of the ligand are revealed by n.m.r. and structural data.     

Synthesis and Structures of Bis(alkene) Complexes of Tungsten and Molybdenum, [M(CO)2(dpphen)(dbf)2] (M = W or Mo; dpphen = 4,7‐diphenyl‐1,10‐phenanthroline; dbf = dibutylfumarate)

Tungsten and molybdenum complexes [M(CO)₂(dpphen)(dbf)₂] (M = W 1 or Mo 2 ; dpphen = 4,7‐diphenyl‐1,10‐phenanthroline; dbf = dibutylfumarate) have been synthesized and structurally characterized by X‐ray diffraction analysis. In both complexes which have similar structure, the metal atom co‐ordination is distorted octahedral with dpphen and two CO groups in the equatorial plane and the metal atom binds in an η²‐fashion to the C–C bonds of two dbf ligands. The two C–C bonds are almost mutually orthogonal. The two complexes are different in conformation which result from face selection of the two dbf ligands for coordination to the metal atom.     

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.     

Darstellung,Kristallstrukturen und Schwingungsspektren von trans‐[Pt(N3)4(ECN)2]2–, E = S,Se

Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N₃)₄(ECN)₂]^2–, E = S, Se By oxidative addition to (n‐Bu₄N)₂[Pt(N₃)₄] with dirhodane in dichloromethane trans‐(n‐Bu₄N)₂[Pt(N₃)₄(SCN)₂] and by ligand exchange of trans(n‐Bu₄N)₂[Pt(N₃)₄I₂] with Pb(SeCN)₂ trans‐(n‐Bu₄N)₂[Pt(N₃)₄(SeCN)₂] are formed. X‐ray structure determinations on single crystals of trans‐(Ph₄P)₂[Pt(N₃)₄(SCN)₂] (triclinic, space group P 1, a = 10.309(3), b = 11.228(2), c = 11.967(2) Å, α = 87.267(13), β = 75.809(16), γ = 65.312(17)°, Z = 1) and trans‐(Ph₄P)₂[Pt(N₃)₄(SeCN)₂] (triclinic, space group P 1, a = 9.1620(10), b = 10.8520(10), c = 12.455(2) Å, α = 90.817(10), β = 102.172(10), γ = 92.994(9)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–S = 2.337, Pt–Se = 2.490 and Pt–N = 2.083 (S), 2.053 Å (Se). The approximate linear Azidoligands with N^α–N^β–N^γ‐angles = 172,1–175,0° are bonded with Pt–N^α–N^β‐angles = 116,7–120,5°. In the vibrational spectra the platinum chalcogen stretching vibrations of trans‐(n‐Bu₄N)₂[Pt(N₃)₄(ECN)₂] are observed at 296 (E = S) and in the range of 186–203 cm^–1 (Se). The platinum azide stretching modes of the complex salts are in the range of 402–425 cm^–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtS) = 1.64, f_d(PtSe) = 1.36, f_d(PtN^α) = 2.33 (S), 2.40 (Se) and f_d(N^αN^β, N^βN^γ) = 12.43 (S), 12.40 mdyn/Å (Se).     

Stufenweise und chemisch reversible Reduktion von Zweikernkomplexen {(μ‐bmtz)[MCl(η6‐Cym)]2}[PF6]2 (M = Ru,Os; bmtz = 3,6‐Bis(2′‐pyrimidyl)1,2,4,5‐tetrazin) mit bis zu sechs Elektronen

Stepwise and Chemically Reversible Reduction of {(μ‐bmtz)[MCl(η⁶‐Cym)]₂}[PF₆]₂ (M = Ru, Os; bmtz = 3,6‐Bis(2′‐pyrimidyl)1,2,4,5‐tetrazine) with up to Six Electrons The title compounds were synthesized and characterized spectroscopically. Analysis of cyclic voltammetry in conjunction with spectroelectrochemistry (UV/VIS/NIR, ESR) allowed us to identify the products of sequential, chemically reversible reduction with up to six electrons. It is the first time that the molecular coupling of electron transfer steps (E) and bond breaking/bond forming chemical processes (C) has been studied for a diruthenium system. In that case, the chemically reversible sequence E, EC, EEC, E and E was observed whereas the diosmium analogue showed the unusual sequence E, EC, E, EEC and E.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.     

Die Kristallstruktur des Diacetonalkohol‐Komplexes [Mn(DAA)3]2+[MnI4]2– · DAA

Crystal Structure of the Diacetone Alcohol Complex [Mn(DAA)₃]²⁺[MnI₄]^2– · DAA The title compound has been prepared from MnI₂ and excess diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanon) to give brown single crystals which were suitable for a crystal structure determination. Space group P2₁/c, Z = 4, lattice dimensions at 157 K: a = 1158.3(1), b = 1806.0(1), c = 1846.5(2) pm, β = 97.421(8)°, R₁ = 0.0381. The structure consists of [Mn(DAA)₃]²⁺ ions with distorted octahedral environment of the manganese atom, tetrahedral [MnI₄]^2– ions and a diacetone alcohol molecule which is connected by two hydrogen bridges with the complex cation.     

Kristallstruktur des Molybdän(V)‐Imido‐Komplexes [MoCl3(NtBu)(H2NtBu)]2 · 1/2 C7H8

Crystal Structure of the Molybdenum(V) Complex [MoCl₃(N^tBu)(H₂N^tBu)]₂ · ¹/₂ C₇H₈ Green moisture sensitive single crystals of [MoCl₃(N^tBu)(H₂N^tBu)]₂ ( 1 · ¹/₂ C₇H₈) have been prepared from molybdenum pentachloride with Me₂Si(HN^tBu)₂ in toluene solution; they were suitable for a crystal structure determination. 1 · ¹/₂ C₇H₈: Space group P 1, Z = 2, lattice dimensions at –83 °C: a = 696.9(1), b = 1470.9(2), c = 1579.0(2) pm, α = 96.673(13)°, β = 92.014(14)°, γ = 94.852(14)°, R = 0.0321. 1 forms centrosymmetric molecules in which the molybdenum atoms are linked by two μ‐Cl‐bridges with MoCl bond lengths of 245.7 and 270.2 pm in average of the two crystallographically independent individuals. The longer MoCl bond is in trans‐position to the nitrogen atom of the imido ligand (MoN distance 169.0 pm, MoNC bond angle 167.0° in average).     

Darstellung,Kristallstrukturen und Schwingungsspektren von trans‐[Pt(N3)4X2]2–, X = Cl,Br, I

Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N₃)₄X₂]^2–, X = Cl, Br, I By oxidative addition to (n‐Bu₄N)₂[Pt(N₃)₄] with the elemental halogens in dichloromethane trans‐(n‐Bu₄N)₂[Pt(N₃)₄X₂], X = Cl, Br, I are formed. X‐ray structure determinations on single crystals of trans‐(Ph₄P)₂[Pt(N₃)₄Cl₂] (triclinic, space group P1, a = 10.352(1), b = 10.438(2), c = 11.890(2) Å, α = 91.808(12), β = 100.676(12), γ = 113.980(10)°, Z = 1), trans‐(Ph₄P)₂[Pt(N₃)₄Br₂] (triclinic, space group P1, a = 10.336(1), b = 10.536(1), c = 12.119(2) Å, α = 91.762(12), β = 101.135(12), γ = 112.867(10)°, Z = 1) and trans‐(Ph₄P)₂[Pt(N₃)₄I₂] (triclinic, space group P1, a = 10.186(2), b = 10.506(2), c = 12.219(2) Å, α = 91.847(16), β = 101.385(14), γ = 111.965(18)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–Cl = 2.324, Pt–Br = 2.472, Pt–I = 2.619 and Pt–N = 2.052–2.122 Å. The approximate linear Azidoligands with N^α–N^β–N^γ‐angles = 172.1–176.8° are bonded with Pt–N^α–N^β‐angles = 116.2–121.9°. In the vibrational spectra the platinum halogen stretching vibrations of trans‐(n‐Bu₄N)₂[Pt(N₃)₄X₂] are observed in the range of 327–337 (X = Cl), at 202 (Br) and in the range of 145–165 cm^–1 (I), respectively. The platinum azide stretching modes of the three complex salts are in the range of 401–421 cm^–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl) = 1.90, f_d(PtBr) = 1.64, f_d(PtI) = 1.22, f_d(PtN^α) = 2.20–2.27 and f_d(N^αN^β, N^βN^γ) = 12.44 mdyn/Å.     

Synthese und Struktur von [(Ph3PAu)3NPPh3][PF6]2, einem Gold(I)‐phosphoraniminato‐Komplex

Synthesis and Crystal Structure of [(Ph₃PAu)₃NPPh₃][PF₆]₂, a Gold(I) Phosphoraneiminato Complex The photolytic reaction of Ph₃PAuN₃ with Cr(CO)₆ in THF yields the phosphoraneiminato complex [(Ph₃PAu)₃NPPh₃]²⁺ in low yield as well as the cluster cation [(Ph₃PAu)₈]²⁺ as the main product. The phosphoraneiminato complex crystallizes from CH₂Cl₂ with [PF₆]^? ions as [(Ph₃PAu)₃NPPh₃][PF₆]₂·CH₂Cl₂ in the triclinic space group with a = 1200.8(1), b = 1495.6(2), 2053.5(5), α = 86.97(2)°, β = 82.79(1)°, γ = 81.87(2)°, and Z = 2. The phosphoraneiminato ligand bridges through its N atom three Au atoms, which itself are connected to each other by weak aurophilic interactions.     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.     

Darstellung und Strukturen von (η6‐Diaren)TiII‐bis(tetrachloroaluminat)Komplexen,Diaren = Biphenyl oder 3,5,3′,5′‐Tetramethyl‐biphenyl

Syntheses and Crystal Structures of (η⁶‐Diarene)Ti^II‐bis(tetrachloroaluminate) Complexes, Diarene = Biphenyl or 3,5,3′,5′‐Tetramethyl‐biphenyl Syntheses of (η⁶‐diarene)Ti^II(AlCl₄)₂ complexes were performed by the Fischer‐Hafner method. The diarenes employed were biphenyl and 3,5,3′,5′‐tetramethyl‐biphenyl. In each of the resulting complexes, (η⁶‐C₁₂H₁₀)Ti^II(AlCl₄)₂ ( 1 ) and (η⁶‐C₁₆H₁₈)Ti^II(AlCl₄)₂ ( 2 ), only one C₆‐ring of a diarene is coordinatively active. 1 : Space group Pbca, Z = 8, lattice constants at 20 °C: a = 16.864(3), b = 13.931(3), c = 18.807(3) Å; R₁ = 0.048. 2 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 9.775(1), b = 13.720(1), c = 20.214(1) Å; β = 95.50(1)°; R₁ = 0.050.