[Ph2P(O)CH2Im][F3B(μ‐OH)BF3]. Erste strukturanalytische Charakterisierung des Hexafluoro(μ‐hydroxo)diborat‐Ions [1]

[Ph₂P(O)CH₂Im][F₃B(μ‐OH)BF₃]. First Structural Characterization of the Hexafluoro(μ‐hydroxo)diborate Ion [1] The hexafluoro(μ‐hydroxo)diborate ion has been isolated as it's Ph₂P(O)CH₂Im salt [Im = 2‐(1, 3, 4, 5‐tetramethylimidazolio)] ( 2 ) through basic hydrolysis of [Ph₂P(OBF₃)CH₂Im]BF₄ ( 1 ). The crystal structure of 2 · CH₂Cl₂ reveals the presence of ion pairs linked by unsymmetrical O‐H‐O hydrogen bonds.     

Synthese und Deprotonierung eines Phosphinomethylimidazoliumsalzes. Zur Delokalisierung der π‐Elektronen in Aminovinylphosphanen [1]

Tetrafluorobo‐Synthesis and Deprotonation of a Phosphinomethylimidazolium Salt. On the π‐Electron Delocalization im Aminovinyl Phosphanes [1] The ylidic olefin 1, 3, 4, 5‐tetramethyl‐2‐methyleneimidazoline ( 1 , Im=CH₂) reacts with chlorodiphenylphosphane to give the phosphane salt [(Im‐CH₂)PPh₂]Cl ( 6 ) from which the vinylphosphane Im=CHPPh₂ ( 8 ) is obtained by deprotonation. 8 reacts with HBF₄ etherate to give the tetrafluoroborate salt [(Im‐CH₂)‐PPh₂] BF₄ ( 7 ). The crystal structures of 7 and 8 are determined and discussed. In 8 , π‐electron delocalisation is indicated both by structural data and temperature dependent n.m.r. spectroscopy     

Germanium(II)‐, Zinn(II)‐ und Blei(II)‐Derivate des polycyclischen Alumosiloxans [Ph2SiO]8[Al(O)OH]4

Germanium(II)‐, Tin(II)‐ and Lead(II)‐Derivatives of the polycyclic Alumosiloxane [Ph₂SiO]₈[Al(O)OH]₄ Five new derivatives of the polycyclic alumosiloxane [Ph₂SiO]₈[Al(O)OH]₄ have been synthesized by replacement of the protic hydrogen atoms on the hydroxy‐groups attached to the aluminium atoms by the divalent group 14 elements germanium, tin and lead. The compounds can be divided in those with one metal atom per alumosiloxane moiety, [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]M (M=Ge, Sn), and those with complete substitution of the protic hydrogen atoms by metal atoms like [Ph₂SiO]₈[AlO₂]₄M₂ (M= Sn, Pb). Always one element of the series Ge, Sn, Pb is missing in the two types of compounds. Crystal structure analyses of [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]₂M · 2 C₄H₈O₂ (M= Ge ( 1 ), Sn ( 2a )), [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]₂Sn · 2 THF ( 2b ) and [Ph₂SiO]₈[AlO₂]₄M₂ (M= Sn ( 3 ), Pb ( 4 )) have been performed elucidating either polycyclic basket‐type ( 1 , 2a , 2b ) or closed polyhedral structures ( 3 , 4 ).     

Oxorhenium(V) Complexes with 1,3,4‐Triphenyl‐1,2,4‐triazol‐5‐ylidene

Reactions of the oxorhenium(V) complexes [ReOX₃(PPh₃)₂] (X = Cl, Br) with the N‐heterocyclic carbene (NHC) 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (L^Ph) under mild conditions and in the presence of MeOH or water give [ReOX₂(Y)(PPh₃)(L^Ph)] complexes (X = Cl, Br; Y = OMe, OH). Attempted reactions of the carbene precursor 5‐methoxy‐1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazole ( 1 ) with [ReOCl₃(PPh₃)₂] or [NBu₄][ReOCl₄] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such as [HL^Ph][ReOCl₄(OPPh₃)], [HL^Ph][ReOCl₄(OH₂)] or [HL^Ph][ReO₄] were isolated. The neutral [ReOX₂(Y)(PPh₃)(HL^Ph)] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis‐position to PPh₃. The relatively long Re–C bond lengths of approximate 2.1Å indicate metal‐carbon single bonds.     

Zur Reaktivität von dinuklearen Platina‐β‐diketonen gegenüber Phosphanen: Diacetylplatin(II)‐Komplexe und mononukleare Platina‐β‐diketone

The Reactivity of Dinuclear Platina‐β‐diketones with Phosphines: Diacetylplatinum(II) Complexes and Mononuclear Platina‐β‐diketones Addition of mono‐ and bidentate phosphines or of AsPh₃ to the platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) followed by the addition of NaOMe at ?70 °C resulted in the formation of diacetyl platinum(II) complexes cis‐[Pt(COMe)₂L₂] (L = PPh₃, 2a ; P(4‐FC₆H₄)₃, 2b ; PPh₂(4‐py), 2c ; PMePh₂, 2d ; AsPh₃, 2d ) and [Pt(COMe)₂(L??L)] (L??L = dppe, 3b ; dppp, 3c ), respectively. The analogous reaction with dppm afforded the dinuclear complex cis‐[{Pt(COMe)₂}₂(μ‐dppm)₂] ( 4 ) that reacted in boiling acetone yielding [Pt(COMe)₂(dppm)] ( 3a ). The reactions 1 → 2 / 3 were found to proceed via thermally highly unstable cationic mononuclear platina‐β‐diketone intermediates [Pt{(COMe)₂H}L₂]⁺ and [Pt{(COMe)₂H}(L??L)]⁺, respectively, that could be isolated as chlorides for L??L = dppe ( 5a ) and dppp ( 5b ). The reversibility of the deprotonation of type 5 complexes with NaOMe yielding type 3 complexes was shown by the protonation of the diacetyl complex 3b with HBF₄ yielding the platina‐β‐diketone [Pt{(COMe)₂H}(dppe)](BF₄) ( 5c ). All compounds were fully characterized by means of NMR and IR spectroscopies, and microanalyses. X‐ray diffraction analysis was performed for the complex cis‐[Pt(COMe)₂(PPh₃)₂]·H₂O·CHCl₃ ( 2a ·H₂O·CHCl₃).     

Metallabis(phosphonate) als Chelatliganden. I. Synthese einkerniger Nickelbis(phosphonat)–Komplexe mit OHO-Wasserstoffbrücke und entsprechender Alkali-metall-, Ammonium- und Thallium-Verbindungen

Nickelocen reagiert mit Dialkylphosphiten HP(O)(OR)₂ zu den Komplexen C₅H₅Ni[{P(OR)₂O}₂H] ( 1 :R ? Me; 2 :R ? Et), in denen ein sechsgliedriger NiP₂O₂H-Ring mit einer vermutlich symmetrischen OHO-Wasserstoffbrücke vorliegt. Die Umsetzung von 1 mit HBF₄ führt zu C₅H₅Ni[{P(OMe)₂O}₂BF₂] ( 3 ). Mit NH₃ und Thalliumacetylacetonat entstehen aus 1 bzw. 2 die Komplexe [C₅H₅Ni{P(OR)₂O}₂]NH₄ ( 4, 5 ) und [C₅H₅Ni{P(OR)₂O}₂]Tl ( 6, 7 ). Die entsprechenden Alkalimetallverbindungen [C₅H₅Ni{P(OMe)₂O}₂]M ( 8 :M ? Li; 9 :M ? Na) sind ausgehend von C₅H₅Ni[P(OMe)₃][P(O)(OMe)₂] und LiI bzw. NaI zugänglich. C₅H₅Ni[P(OMe)₃][P(O)(OMe)₂] reagiert mit HgI₂ zu C₅H₅Ni[P(OMe)₃]I und [IHg{P(O)(OMe)₂}]₂. Metallabisphosphonates as Chelating Ligands. I. Synthesis of Mononuclear Nickelbisphosphonates Containing a OHO-Hydrogen Bridge and of Corresponding Alkali Metal, Ammonium, and Thallium Compounds Nickelocene reacts with dialkylphosphites HP(O)(OR)₂ to form the complexes C₅H₅Ni[{P(OR)₂O}₂H] ( 1 :R ? Me; 2 :Et) which contain a six-membered NiP₂O₂H ring with a presumably symmetrically OHO-hydrogen bond. The reaction of 1 with HBF₄ leads to C₅H₅Ni?[{P(OMe)₂O}₂BF₂] ( 3 ). The complexes 1 and 2 react with NH₃ and thallium acetylacetonate to give [C₅H₅Ni{P(OR)₂O}₂]NH₄ ( 4, 5 ) and [C₅H₅Ni{P(OR)₂O}₂]Tl ( 6, 7 ), respectively. The corresponding alkali metal compounds [C₅H₅Ni{P(OMe)₂O}₂]M ( 8 :M ? Li; 9 :M ? Na) are formed in the reaction of C₅H₅Ni[P(OMe)₃][P(O)(OMe)₂] with LiI or NaI. With HgI₂, C₅H₅Ni[P(OMe)₃][P(O)(OMe)₂] reacts to yield C₅H₅Ni[P(OMe)₃]I and [IHg{P(O)(OMe)₂}]₂.     

Kristallstrukturelle,Festkörper‐31P‐CP/MAS‐NMR,TOSS, 31P‐COSY‐NMR und mechanistische Beiträge zur Koordinationschemie des Octacarbonyldicobalts mit den Liganden Bis(diphenylphosphanyl)amin,Bis(diphenylphosphanyl)methan und 1,1,1‐Tris(diphenylphosphanyl)ethan

Chemistry of Polyfunctional Molecules. 133. X‐Ray Crystal Structural, Solid‐state ³¹P CP/MAS NMR, TOSS, ³¹P COSY NMR, and Mechanistic Contributions to the Co‐ordination Chemistry of Octacarbonyldicobalt with the Ligands Bis(diphenylphosphanyl)amine, Bis(diphenylphosphanyl)methane, and 1,1,1‐Tris(diphenylphosphanyl)ethane Co₂(CO)₈ reacts with bis(diphenylphosphanyl)amine, HN(PPh₂)₂ (Hdppa, 1 ), in two steps to afford the known compound [Co(CO)(Hdppa‐κ²P)₂][Co(CO)₄] · 2 THF ( 6 a · 2 THF). The intermediate [Co(CO)₂(Hdppa‐κ²P) · (Hdppa‐κP)][Co(CO)₄] · dioxane · n‐pentane ( 5 · dioxane · n‐pentane) was isolated for the first time and was characterized by X‐ray analysis. The cation 5 ⁺ exhibits a slightly distorted trigonal‐bipyramidal geometry. Detailed ³¹P‐NMR investigations (solid‐state CP/MAS NMR, TOSS, ³¹P‐COSY, ³¹P‐EXSY) showed that the additional tautomer [Co(CO)₂(Hdppa‐κ²P)(Ph₂P–N=P(H)Ph₂‐κP)]⁺ ( 5 ′⁺) is present in solution. The tautomer equilibrium is slow in the NMR time scale. In contrast to the solid state only tetragonal pyramidal species of 5 are found in solution. At –90 °C there is slow exchange between the three diastereomeric species 5 a ⁺– 5 c ⁺. Compound 5 forms [Co(CO) · (Hdppa‐κ²P)₂]BPh₄ · THF ( 6 b · THF) in THF with NaBPh₄ under CO‐Elimination. A X‐ray diffraction investigation shows that the cation 6 ⁺ consists of a slightly distorted trigonal‐bipyramidal co‐ordination polyeder. However, a distorted tetragonal‐pyramidal structure has been found for the cation 7 ⁺ of the related compound [Co(CO)(dppm)₂][Co(CO)₄] · 2 THF ( 7 · 2 THF; dppm = bis(diphenylphosphanyl)methane, Ph₂PCH₂PPh₂). A comparison with the known [8] trigonal‐bipyramidal stereoisomer, ascertained for 7 ⁺ of the solvent‐free 7 , is described. In solutions of 6 a · 2 THF and 7 · 2 THF ¹³C{¹H}‐ and ³¹P{¹H}‐NMR spectra indicate an exchange of all CO and organophosphane molecules between cobalt(I) cation and cobalt(–I) anion. A concerted mechanism for the exchange process is discussed. CO elimination leads to discontinuance of the cyclic mechanism by forming binuclear substitution products such as the isolated Co₂(CO)₂ · (μ‐CO)₂(μ‐dppm)₂ · 0.83 THF ( 8 · 0.83 THF), which was characterized by spectroscopy and X‐ray analysis. For the dissolved [Co(CO)₂CH₃C(CH₂PPh₂)₃][Co(CO)₄] · 0.83 n‐pentane ( 9 a · 0.83 n‐pentane) no CO and triphos exchange processes between the cation and the anion are observed. Metathesis of 9 a · 0.83 n‐pentane with NaBPh₄ yields [Co(CO)₂CH₃C(CH₂PPh₂)₃]BPh₄ ( 9 b ) which has been characterized by single‐crystal X‐ray analysis. The cation shows a small distorted tetragonal‐pyramidal structure.     

Reaction of the Pincer‐type Ligand {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu‐C6H2}— with [Ph3C]+[PF6]—. Unprecedented Rearrangement and Carbon‐Carbon Bond Formation

The reaction of the organolithium derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu‐C₆H₂}Li ( 1 ‐Li) with [Ph₃C]⁺[PF₆]^— gave the substituted biphenyl derivative 4‐[(C₆H₅)₂CH]‐4′‐[tert‐Bu]‐2′, 6′‐[P(O)(OEt)₂]₂‐1, 1′‐biphenyl ( 5 ) which was characterized by ¹H, ¹³C and ³¹P NMR spectroscopy and single crystal X‐ray analysis. Ab initio MO‐calculations reveal the intramolecular O···C distances in 5 of 2.952(4) and 2.988(5)Å being shorter than the sum of the van der Waals radii of oxygen and carbon to be the result of crystal packing effects. Also reported are the synthesis and structure of the bromine‐substituted derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu]C₆H₂}Br ( 9 ) and the structure of the protonated ligand 5‐tert‐Bu‐1, 3‐[P(O)(OEt)₂]₂C₆H₃ ( 1 ‐H). The structures of 1 ‐H, 5 , and 9 are compared with those of related metal‐substituted derivatives.     

On the Reactivity of the Platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] Towards Ph2PCH2CH2CH2SOxPh (x = 0, 2)

The reaction of the electronically unsaturated platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) with Ph₂PCH₂CH₂CH₂SPh ( 2 ) leads selectively to the formation of the acetyl(chlorido) platinum(II) complex (SP‐4‐3)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 4 ) having the γ‐phosphinofunctionalized propyl phenyl sulfide coordinated in a bidentate fashion (κP,κS). In boiling benzene complex 4 undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex (SP‐4‐3)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 6 ). However, the reaction of 1 with the analogous γ‐diphenylphosphinofunctionalized propyl phenyl sulfone Ph₂PCH₂CH₂CH₂SO₂Ph ( 3 ) affords the acetyl(chlorido) platinum(II) complex (SP‐4‐4)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 5 ). In boiling benzene complex 5 undergoes a CO extrusion yielding (SP‐4‐4)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 8 ) whereas in presence of 1 the formation of the carbonyl complex (SP‐4‐3)‐[PtMeCl(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)] ( 7 ) is observed. Addition of Ag[BF₄] to complex 5 leads to the formation of the cationic methyl(carbonyl) platinum(II) complex (SP‐4‐1)‐[PtMe(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂][BF₄] ( 9 ). All complexes were characterized by microanalysis and NMR spectroscopy (¹H, ¹³C, ³¹P) and complexes 4 and 6 additionally by single‐crystal X‐ray diffraction analyses.     

Tetraphenylphosphonium bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)aurate(III) acetone solvate and ethyltriphenylphosphonium bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato)aurate(III)

In the two title complexes, (C₂₄H₂₀P)[Au(C₃S₅)₂]·C₃H₆O, (I), and (C₂₀H₂₀P)[Au(C₃S₅)₂], (II), the Au^III atoms exhibit square‐planar coordinations involving four S atoms from two 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate (dmit) ligands. The Au—S bond lengths, ranging from 2.3057 (8) to 2.3233 (7) Å in (I) and from 2.3119 (8) to 2.3291 (10) Å in (II), are slightly smaller than the sum of the single‐bond covalent radii. In (I), there are two halves of independent Ph₄P⁺ cations, in which the two P atoms lie on twofold rotation axis sites. The Ph₄P⁺ cations and [Au(C₃S₅)₂]⁻ anions are interspersed as columns in the packing. Layers composed of Ph₄P⁺ and [Au(C₃S₅)₂]⁻ are separated by layers of acetone molecules. In (II), the [Au(C₃S₅)₂]⁻ anions and EtPh₃P⁺ counter‐cations form a layered arrangement, and the [Au(C₃S₅)₂]⁻ anions form discrete pairs with a long intermolecular Au...S interaction for each Au atom in the crystal structure.     

Die Reaktion von SePh2 mit N‐Chlorsuccinimid. Kristallstrukturen von [SeCl2Ph2] und [SeCl2Ph2(Succinimid)2]

Reaction of SePh₂ with N‐Chlorosuccinimide. Crystal Structures of [SeCl₂Ph₂] and [SeCl₂Ph₂(succinimide)₂] SePh₂ reacts with N‐chlorosuccinimide in acetonitrile solution to give [SeCl₂Ph₂] ( 1 ) and [SeCl₂Ph₂(succinimide)₂] ( 2 ) as colourless crystals, which can be separated by fractional crystallization. According to X‐ray single crystal determinations both compounds contain [SeCl₂Ph₂] molecules with ψ‐trigonal‐bipyramidal coordination at the selenium atom, the chloro ligands being in apical positions. In 2 the dimeric unit (HNC₄O₂H₄)₂ is linked with its [SeCl₂Ph₂] unit via a weak C–H···O hydrogen bond. 1 : Space group Pbcn, Z = 4, lattice dimensions at 193 K: a = 1350.6(1), b = 573.3(1), c = 1503.3(2) pm, R₁ = 0.0326. 2 : Space group I2/a, Z = 4, lattice dimensions at 193 K: a = 1363.9(1), b = 557.7(1), c = 2781.3(1) pm, β = 101.01(1)°, R₁ = 0.0286.     

Decamethyl­ferrocenium bis­(2‐oxo‐1,3‐dithiole‐4,5‐dithiolato‐κ2S4,S5)nickelate(III) tetra­hydro­furan solvate

The title compound, [Fe(C₁₀H₁₅)₂][Ni(C₃OS₄)₂]·C₄H₈O or [Fe(Cp*)₂][Ni(dmio)₂]·THF, where [Fe(Cp*)₂]⁺ is the deca­methyl­ferrocenium cation, dmio is the 2‐oxo‐1,3‐dithiole‐4,5‐dithiol­ate dianion and THF is tetra­hydro­furan, crystallizes with two independent half‐anion units [one Ni atom is at the centre of symmetry (, , 0) and the other is at the centre of symmetry (, 0, )], one cation unit (located in a general position) and one THF solvent mol­ecule in the asymmetric unit. The crystal structure consists of two‐dimensional layers composed of parallel mixed chains, where pairs of cations alternate with single anions. These layers are separated by sheets of anions and THF mol­ecules.     

Synthesis and characterizations of N,N′‐bis(diphenylphosphino)‐2‐(aminomethyl)aniline derivatives: application of a palladium(II) complex as pre‐catalyst in Heck and Suzuki cross‐coupling reactions

The reaction of 2‐(aminomethyl)aniline with 2 equivalents of PPh₂Cl in the presence of Et₃N, proceeds in CH₂Cl₂ to give N,N′‐bis(diphenylphosphino)‐2‐(aminomethyl)aniline 1 in good yield. Oxidation of 1 with aqueous H₂O₂, elemental sulfur or gray selenium gave the corresponding oxide, sulfide and selenide dichalcogenides [Ph₂P(E)NHC₆H₄CH₂NHP(E)Ph₂] (E: O, 2a; S, 2b; Se, 2c), respectively. The reaction of [Ph₂PNHC₆H₄CH₂NHPPh₂] with PdCl₂(cod), PtCl₂(cod) and [Cu(MeCN)₄]PF₆ gave the corresponding chelate complexes, PdCl₂1, PtCl₂1 and [Cu(1)₂]PF₆. The new compounds were fully characterized by NMR, IR spectroscopy and elemental analysis. The catalytic activity of the Pd(II) complex was tested in the Suzuki coupling and Heck reactions. The Pd(II) complex catalyzes the Suzuki coupling and Heck reaction, affording biphenyls and stilbenes respectively, in good yields. Copyright © 2009 John Wiley & Sons, Ltd.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Base‐Stabilized [PO]+/[PO2]+ Cations

The salts [(BAC)₂PO][BF₄] ( 5 ) and [(BAC)₂PO₂][BF₄] ( 4 ) (BAC=bis(diisopropylamino) cyclopropenylidene), consisting of the PO⁺ and PO₂⁺ cations, respectively, coordinated to the singlet carbenes, have been prepared. Computational investigations reveal that the electronic structure of the PO⁺ cation is a hybrid between the charge‐localized and charge‐delocalized resonance forms, resulting in ambiphilic reactivity. Compound 5 reacts as a donor with the transition‐metal complex K₂PtCl₄ to furnish [[(BAC)₂PO]₂PtCl₂][BF₄]₂ ( 6 ) and KCl. Remarkably, both 5 and 4 have shown to act as electrophiles undergoing reactions with fluoride anion, leading to [OPF₂]^? and (BAC)PO₂F, respectively.     

Chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ2P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate

The aminophosphane ligand 1‐amino‐2‐(diphenylphosphanyl)ethane [Ph₂P(CH₂)₂NH₂] reacts with dichloridotris(triphenylphosphane)ruthenium(II), [RuCl₂(PPh₃)₃], to form chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ²P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate, [RuCl(C₁₈H₁₅P)(C₁₄H₁₆NP)₂]Cl·C₇H₈ or [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]Cl·C₇H₈. The asymmetric unit of the monoclinic unit cell contains two molecules of the Ru^II cation, two chloride anions and two toluene molecules. The Ru^II cation is octahedrally coordinated by two chelating Ph₂P(CH₂)₂NH₂ ligands, a triphenylphosphane (PPh₃) ligand and a chloride ligand. The three P atoms are meridionally coordinated, with the Ph₂P– groups from the ligands being trans. The two –NH₂ groups are cis, as are the chloride and PPh₃ ligands. This chiral stereochemistry of the [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]⁺ cation is unique in ruthenium–aminophosphane chemistry.     

2‐Amino‐5‐(2‐pyridyl)‐thiadiazole as Bidentate Ligand

The amino substituted bidentate chelating ligand 2‐amino‐5‐(2‐pyridyl)‐1,3,4‐thiadiazole (H₂ L ) was used to prepare 3:1‐type coordination compounds of iron(II), cobalt(II) and nickel(II). In the iron(II) perchlorate complex [Fe^II(H₂ L )₃](ClO₄)₂·0.6MeOH·0.9H₂O a 1:1 mixture of mer and fac isomers is present whereas [Fe^II(H₂ L )₃](BF₄)₂·MeOH·H₂O, [Co^II(H₂ L )₃](ClO₄)₂·2H₂O and [Ni^II(H₂ L )₃](ClO₄)₂·MeOH·H₂O feature merely mer derivatives. Moessbauer spectroscopy and variable temperature magnetic measurements revealed the [Fe^II(H₂ L )₃]²⁺ complex core to exist in the low‐spin state, whereas the [Co^II(H₂ L )₃]²⁺ complex core resides in its high‐spin state, even at very low temperatures.     

Iodoplumbate mit vier‐ und fünffach koordinierten Pb2+‐Ionen

Iodoplumbates with Tetra‐ and Penta‐coordinated Pb²⁺ Ions In contrast to all known iodoplumbates with octahedrally coordinated Pb²⁺ ions, square pyramidal geometry is observed in the iodoplumbate chains of (Pr₄N)[PbI₃] ( 1 ) and [Mg(dmf)₆][PbI₃]₂ ( 2 ), whereas the isolated anions in (Ph₄P)₂[Pb₂I₆] ( 3 ) and [Bu₃N–(CH₂)₃–NBu₃][PbI₄] ( 4 ) contain tetra‐coordinated lead atoms. (Pr₄N)[PbI₃] ( 1 ): a = 910.86(6), b = 1221.46(7), c = 1907.7(1) pm, V = 2122.5(2) · 10⁶ pm³, space group P2₁2₁2₁; [Mg(dmf)₆][PbI₃]₂ ( 2 ): a = 891.24(9), b = 1025.34(7), c = 1234.82(9) pm, α = 92.938(8), β = 106.457(8), γ = 98.100(7)°, V = 1066.4(2) · 10⁶ pm³, space group P1; (Ph₄P)₂[Pb₂I₆] ( 3 ): a = 1174.5(1), b = 722.29(7), c = 3104.8(4) pm, β = 100.50(1)°, V = 2589.8(5) · 10⁶ pm³, space group P2₁/n; [Bu₃N–(CH₂)₃–NBu₃][PbI₄] ( 4 ): a = 2178.3(1), b = 1008.63(5), c = 1888.3(1) pm, β = 110.003(5)°, V = 3898.6(4) · 10⁶ pm³, space group P2/c.     

Bis(1,2‐diselenoquadratato)metallate

Bis(1,2‐diselenosquarato) Metalates A series of 1,2‐diselenosquarato metalates [M(dssq)₂]^2– (M = Pd²⁺, Pt²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Pb²⁺, VO²⁺) was available by direct synthesis from the appropriate metal salt with dipotassium 1,2‐diselenosquarate in deoxygenized water under an argon athmosphere. The copper(II)complex, [Cu(dssq)₂]^2–, and the oxovanadium(IV)complex, [VO(dssq)₂]^2–, were identified in solution by EPR spectroscopy (parameters: [Cu(dssq)₂]^2–: g₀ = 2.073; a = –76.0 · 10^–4 cm^–1, a = 47.0 · 10^–4 cm^–1; [VO(dssq)₂]^2–: g₀ = 1.986; a = 74.9 · 10^–4 cm^–1). The complexes bis(tetraphenylphosphonium)[bis(1,2‐diselenosquarato)nickelate(II)], (Ph₄P)₂[Ni(dssq)₂], and bis(tetraphenylphosphonium)[bis(1,2‐diselenosquarato)zincate(II)], (Ph₄P)₂[Zn(dssq)₂], were characterized by X‐ray structure analysis. The square‐planar Ni^II complex (Ph₄P)₂[Ni(dssq)₂] crystallizes in the monoclinic spacegroup P2₁/n with the unit cell parameters a = 11.1472(8) Å, b = 15.331(1) Å, c = 14.783(1) Å, β = 94.441(1)° and Z = 2. The Zn^II‐complex (Ph₄P)₂[Zn(dssq)₂] is tetrahedral coordinated and crystallizes in the monoclinic spacegroup P2₁/c with the unit cell parameters a = 9.4238(1) Å, b = 18.5823(3) Å, c = 29.5309(5) Å, β = 96.763(1)° and Z = 4.     

N‐Methylimidazolkomplexe des Berylliums: [Be(Me‐Im)4]I2 und [Be3(μ‐OH)3(Me‐Im)6]Cl3

Tetra(N‐methylimidazole)‐beryllium‐di‐iodide, [Be(Me‐Im)₄]I₂ ( 1 ), was prepared from beryllium powder and iodine in N‐methylimidazole suspension to give yellow single crystal plates, which were characterized by X‐ray diffraction and IR spectroscopy. Compound 1 crystallizes tetragonally in the space group I 2d with four formula units per unit cell. Lattice dimensions at 100(2) K: a = b = 1784.9(1), c = 696.2(1) pm, R₁ = 0.0238. The structure consists of homoleptic dications [Be(Me‐Im)₄]²⁺ with short Be–N distances of 170.3(3) pm and iodide ions with weak interionic C–H ··· I contacts. Experiments to yield crystalline products from reactions of N‐methylimidazole with BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively, in dichloromethane solutions were unsuccessful. However, single crystals of [Be₃(μ‐OH)₃(Me‐Im)₆]Cl₃ ( 2 ) were obtained from these solutions in the presence of moisture air. According to X‐ray diffraction studies, two different crystal individuals ( 2a and 2b ) result, depending on the starting materials BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively [ 2a : Space group P2₁/n, Z = 4; 2b : Space group P , Z = 2]. As a side‐product from the reaction of N‐methylimidazole with (Ph₄P)₂[Be₂Cl₆] single crystals of (Ph₄P)Cl·CH₂Cl₂ ( 3 ) were identified crystallographically (P2₁/n, Z = 4) which are isotypical with the corresponding known bromide (Ph₄P)Br·CH₂Cl₂.