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.     

Cluster chemistry. 61. Addition of HX (XCl,Br,I) or AuCl(PPh3) to an open Ru5 cluster. X-ray structures of Ru5(μ-H)(μ5-C2PPh2)(μ-PPh2)(μ-Br)(CO)13 and Ru5(μ-H)(μ5-C2PPh2)(μ3-I)(μ-PPh2)(CO)12

Reactions of aqueous HX (X?Cl, Br) or of AuCl(PPh₃) with Ru₅(μ₅-C₂PPh₂)(μ-PPh₂)(CO)₁₃ result in addition of the 4e-donor set (H + X) or (Au(PPh₃) + Cl) with concomitant opening of two Ru? Ru bonds to give complexes containing dimetallated triangular of ‘scorpion’ cores. Aqueous HI reacts similarly, but in this case the iodide ligand spans three Ru atoms, the (H + I) set acting as 6e-donor. The structures of the two title compounds were confirmed by X-ray crystallographic studies. Ru₅(μ-H)(μ₅-C₂PPh₂)(μ-PPh₂)-(μ-Br)(CO)₁₃ is triclinic, space group P1 , a = 9.689(2), b = 11.874(2), c = 20.005(4) Å, α = 84.66(2), β = 82.90(6), λ = 67.51(6)°, Z = 2; 6478 data with I > 2σ(I) were refined to R = 0.0368, R_w = 0.0362. Ru₅(μ-H)(μ₅-C₂PPh₂)(μ₃-I)(μ-PPh₂)-(CO)₁₂.CH₂Cl₂ is monoclinic, space group P2₁/n, a = 14.809(4), b = 20.721(4), c = 17.698(5) Å, β = 111.42(2)°, Z = 4; 7815 data with I > 2σ(I) were refined to R = 0.0440, R_w = 0.0416.     

Darstellung,Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrochlorid (C6H5)3PO · HCl

On Phosphazo Compounds from Nitriles. IV. The Reaction of Tri, Di, and Monochloroacetonitrile with [Cl₃P?N? PCl₃]Cl. Improved Preparation of [Cl₃P?N? PCl₃]Cl Trichloroacetonitrile reacts with P₂NCl₇ to give Cl₃C? CCl₂? N?PCl₂? N?PCl₃ I , dichloroacetonitrile to give Cl₂C?CCl? N?PCl₂? N?PCl₃ II , and chloroacetonitrile to give the ring compound III . Preparation, n.m.r. and mass spectra of the new compounds are described. The mechanism of formation is discussed. An improved procedure for the preparation of P₂NCl₇ is given.     

[Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthese,Kristallstruktur und Koordinationsisomerie

[Fe₂(μ_sb‐CO)(CO)₃(NO)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)]: Synthesis, X‐ray Crystal Structure and Isomerization Na[Fe₂(μ‐CO)(CO)₆(μ‐P^tBu₂)] ( 1 ) reacts with [NO][BF₄] at —60 °C in THF to the nitrosyl complex [Fe₂(CO)₆(NO)(μ‐P^tBu₂)] ( 2 ). The subsequent reaction of 2 with phosphanes (L) under mild conditions affords the complexes [Fe₂(CO)₅(NO)L(μ‐P^tBu₂)], L = PPh₃, ( 3a ); η‐dppm (dppm = Ph₂PCH₂PPh₂), ( 3b ). In this case the phosphane substitutes one carbonyl ligand at the iron tetracarbonyl fragment in 2 , which was confirmed by the X‐ray crystal structure analysis of 3a . In solution 3b loses one CO ligand very easily to give dppm as bridging ligand on the Fe‐Fe bond. The thus formed compound [Fe₂(CO)₄(NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ) occurs in solution in different solvents and over a wide temperature range as a mixture of the two isomers [Fe₂(μ_sb‐CO)(CO)₃(NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4a ) and [Fe₂(CO)₄(μ‐NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4b ). 4a was unambiguously characterized by single‐crystal X‐ray structure analysis while 4b was confirmed both by NMR investigations in solution as well as by means of DFT calculations. Furthermore, the spontaneous reaction of [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) with NO at —60 °C in toluene yields a complicated mixture of products containing [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 6 ) as main product beside the isomers 4a and 4b occuring in very low yields.     

Darstellung sowie Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrogenfluorid, (C6H5)3PO · HF

Preparation, Crystal and Molecular Structure of Triphenylphosphineoxide Hydrogen - fluoride (C₆H₅)₃PO · HF (C₆H₅)₃PO · HF was prepared from hydrofluoric acid (40%) and (C₆H₅)₃PO in benzene. It crystallizes in the monoclinic space group P2₁/c with a = 1 032.8(3), b = 1 051.0(7), c = 1695.5(2) pm, β = 121.95(2)° and Z = 4; d (calc./obs.) 1.27/1.26 g ° cm^?3. The structure was determined by direct methods from 2 709 independent reflections and has been refined by full matrix least squares methods to R = 0.049. In the compound HF and (C₆H₅)₃PO are linked by a short H-bond. Some distances: O? F 238.4(5), O? H 142.3, H? F 99.8, P? O 149.5(4) pm. Angle O? H? F 159.8°.     

Koordinativ ungesättigte Dieisenkomplexe: Synthese und Kristallstrukturen von [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]

Coordinatively Unsaturated Diiron Complexes: Synthesis and Crystal Structures of [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] and [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] [Fe₂(μ‐CO)(CO)₆(μ‐H)(μ‐P^tBu₂)] ( 1 ) reacts spontaneously with dppm (dppm = Ph₂PCH₂PPh₂) to give [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 2 c ). By thermolysis or photolysis, 2 c loses very easily one carbonyl ligand and yields the corresponding electronically and coordinatively unsaturated complex [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). 3 exhibits a Fe–Fe double bond which could be confirmed by the addition of methylene to the corresponding dimetallacyclopropane [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ). The reaction of 1 with dppe (Ph₂PC₂H₄PPh₂) affords [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppe)] ( 5 ). In contrast to the thermolysis of 2 c , yielding 3 , the heating of 5 in toluene leads rapidly to complete decomposition. The reaction of 1 with PPh₃ yields [Fe₂(CO)₆(H)(μ‐P^tBu₂)(PPh₃)] ( 6 a ), while with ^tBu₂PH the compound [Fe₂(μ‐CO)(CO)₅(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 6 b ) is formed. The thermolysis of 6 b affords [Fe₂(CO)₅(μ‐P^tBu₂)₂] and the degradation products [Fe(CO)₃(^tBu₂PH)₂] and [Fe(CO)₄(^tBu₂PH)]. The molecular structures of 3 , 4 and 6 b were determined by X‐ray crystal structure analyses.     

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.     

Deprotonierung von Mn2(μ-H)(μ-PR2)(CO)8 (R=Ph,Cy) zur Synthese von Heteronuklearen Mangan—Gold Clustern mit Mn2Aun-Kernen (n = 1 – 3)

Deprotonation of Mn₂(μ-H)(μ-PR₂)(CO)₈ (R = Ph Cy) for Synthesis of Heteronuclear Manganese-Gold Clusters with Mn₂Au_n Cores (n = 1–3) The dimanganese complexes Mn₂(μ-H)(μ-PR₂)(CO)₈ (R = Ph, Cy) have been deprotonated with 1,8-diazabicyclo[5.4.0]undec-7-en (DBU) in tetrahydrofuran solution at 20^°C to give the anions [Mn₂(μ-PR₂)(CO)₈]^?, which were isolated as tetraethylammonium salts. Both dimanganese complexes and the related anions were measured by cyclic voltammetry. The treatment of the aforementioned dimanganese complexes in thf solution with Lir' (R =Me, Ph) and subsequently with PPh₃AuCl gave at 20^°C three types of products: Mn₂(μ-PR₂(CO)₈(AuPPh₃),Mn₂(μ-PR₂)(μ-C(R′)O)(CO)₆-(AuPPh₃)₂ and Mn₂(μ-PR₂)(CO)₆(AuPPh₃)₃. The newly prepared substances were characterized by means of IR-, UV/VIS, ³¹P NMR data. The results of single X-ray analyses showed for the three-membered metal ring compound Mn₂(μ-PPh₂)(CO)₈(AuPPh₃) an uni-fold bridged σ(Mn? Mn) bond length of 306.7(3) pm, the metallatetrahedron complex Mn₂(μ-PPh₃)(μ-C(Ph)O(CO)₆(AuPPh₃)₂ a twofold bridged σ(Mn? Mn) bond length of 300.6(4) pm and the trigonal-bipyramidal cluster Mn₂(μ-Pph₂)(CO)₆(AuPPh₃)₃ an uni-fold bridged π(Mn? Mn) bond length of 274.7(3) pm. The Mn? Au bonds of these substances are accompanyied by semi-bridging CO ligands which are signified through short Au…C contact lengths in the range of 251 to 270 pm. In the substance with the Mn₂Au₂ metallatetrahedron core exists, additionally, such a contact with the acylic C atom of C(Ph)O bridging group of 263.4(18) pm. Such contact lengths were compared for corresponding dimanganese and dirhenium complexes.     

Heterometallische Clusterkomplexe der Typen Re2(μ-PR2)(CO)8(HgY) und ReMo(μ-PR2)(η5-C5H5)(CO)6(HgY) (R = Ph,Cy; Y = Cl,W(η5-C5H5)(CO)3)

Heterometallic Cluster Complexes of the Types Re₂(μ-PR₂)(CO)₈(HgY) and ReMo(μ-PR₂)(η⁵-C₅H₅)(CO)₆(HgY) (R = Ph, Cy; Y = Cl, W(η⁵-C₅H₅)(CO)₃) Dinuclear complexes Re₂(μ-H)(μ-PR₂)(CO)₈ and ReMo(μ-H)(μ-PR₂)(η⁵-C₅H₅)(CO)₆ (R = phenyl, cyclohexyl) were deprotonated and reacted as anions with HgCl₂ to compounds of the both types Re₂(μ-PR₂)(CO)₈HgCl) and ReMo(μ-PR₂)(η⁵-C₅H₅)(CO)₆(HgCl). The heterometallic three-membered cluster complexes correspond to an isolobal exchange of a proton against a cationic HgCl⁺ group. For one of the products ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgCl) has been shown its conversion with NaW(η⁵-C₅H₅)(CO)₃ to ReMo(μ-PCy₂)(η⁵-C₅H₅)(HgW(η⁵-C₅H₅)(CO)₃) under substitution of the chloro ligand, par example. The newly prepared compounds were characterized by means of IR, UV/VIS and ³¹P NMR data. A complete determination of the molecular structure by single crystal analyses was done in the case of Re₂(μ-PCy₂)(CO)₈(HgCl) and of ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgCl) which both are dimer because of the presence of an asymmetric dichloro bridge, and of ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgW(η⁵-C₅H₅)(CO)₃). The structural study illustrates through comparison the influence of various metal types on an interaction between centric and edge-bridged frontier orbitals in three-membered metal rings.     

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.     

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.     

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.     

Die Kristall- und Molekülstruktur von Dicäsium- μ-Oxodekafluorodiarsenat

Crystal and Molecular Structure of Dicaesium-μ-Oxodecafluorodiarsenate, Cs₂(As₂F₁₀O) The crystal structure of Cs₂(As₂F₁₀O) has been determined from three-dimensional data. The compound crystallizes in the monoclinic space group P2₁/m, the lattice constants being a = 9.175(4), b = 10.690(5), c = 5.619(3)(Å); β = 105,50(5)°. The anion (As₂F₁₀O)^2– with the point symmetry C_s contains a As? O? As-bridge, whose partial π-bonding is to be discussed. The bond lengths and angles are: As? O: 1.77(2) and 1.68(2) Å, resp., As? O? As: 139(1)°; As…As: 3.225(4) Å, the numbers in parantheses being the standard deviation of the last figure.     

Synthese und Struktur chiraler Heterometallatetrahedrane des Typs [Re2(M1PPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M1 = Ag,Au; M2 = Cu,Ag, Au)

Syntheses and Structure of Chiral Metallatetrahedron Complexes of the Type [Re₂(M¹PPh₃)(M²PPh₃)(μ‐PCy₂)(CO)₇C≡CPh] (M¹ = Ag, Au; M² = Cu, Ag, Au) From the reaction of Li[Re₂(μ‐H)(μ‐PCy₂)(CO)₇(C(Ph)O)] ( 1 ) with Ph₃AuC≡CPh both benzaldehyde and the trinuclear complex Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇C≡CPh] ( 2a ) were obtained in high yield. The complex anion was isolated as its PPh₄‐salt 2b . The latter reacts with coinage metal complexes PPh₃M²Cl [M² = Cu, Ag, Au] to give chiral heterometallatetrahedranes of the general formula [Re₂(AuPPh₃)(M²PPh₃)(μ‐PCy₂)(CO)₇C≡CPh] (M² = Cu 3a , Ag 3b , Au 3c ). The corresponding complex [Re₂(AgPPh₃)₂(μ‐PCy₂)(CO)₇C≡CPh] ( 3d ) is obtained from the reaction of [Re₂(AgPPh₃)₂(μ‐PCy₂)(CO)₇Cl] ( 4 ) with LiC≡CPh. 3d undergoes a metathesis reaction in the presence of PPh₃CuCl giving [Re₂(AgPPh₃)(CuPPh₃)(μ‐PCy₂)(CO)₇C≡CPh] ( 3e ) and PPh₃AgCl. Analogous metathesis reactions are observed when 3c is reacted with PPh₃AgCl or PPh₃CuCl giving 3a or 3b , respectively. The reaction of 1 with PPh₃AuCl gives benzaldehyde and Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Cl] ( 5a ) which upon reaction with PhLi forms the trinuclear complex Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Ph] ( 6a ). Again this complex was isolated as its PPh₄‐salt 6b . In contrast to 2b , 6b reacts with one equivalent of Ph₃PAuCl by transmetalation to give Ph₃PAuPh and PPh₄[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Cl] ( 5b ). The X‐ray structures of the compounds 3a , 3b , 3e and 4 are reported.     

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.     

Kristall- und Molekülstruktur von SbI3 · 9S3 (9S3 = 1,4,7-Trithiacyclononan)

Crystal and Molecular Structure of SbI₃ · 9S3 (9S3 = 1.4.7-Trithiacyclononane) . SbI₃ forms a 1:1 adduct with 1.4.7-trithiacyclononane. The crystal structure exhibits discrete complexes with a distorted octahedral coordination of antimony(III). In comparison with molecular SbI₃ the Sb? I distances are elongated from 271.9 to 290.4 pm (mean). The mean value of the Sb? S distances is 287.5 pm. The planes through iodine and sulfur atoms, respectively, are nearly coplanar. There is no significant stereochemical influence of the Sb(III) lone pair.