Bis(methanol‐κO)dioxido[3,3′‐(1H‐1,2,4‐triazole‐3,5‐diyl)diphenolato‐κ3O,N4,O′]uranium(VI) methanol monosolvate

The structure of the title compound, [U(C₁₄H₉N₃O₂)O₂(CH₃OH)₂]·CH₃OH, is the first to be reported for an actinide complex including triazole ligands. The U^VI atom exhibits a pentagonal–bipyramidal NO₆ coordination environment, involving two axial oxide ligands [U=O = 1.766 (3) and 1.789 (3) Å], four equatorial O atoms [U—O = 2.269 (3)–2.448 (3) Å] from the ligand and the two coordinated methanol molecules, and one equatorial N atom [U—N = 2.513 (4) Å] from the ligand. In the crystal structure, the complex molecules are linked via intermolecular N—H...O and O—H...O hydrogen bonds to form a two‐dimensional structure.     

Chirale Halbsandwich‐Pentamethylcyclopentadienyl‐Rhodium(III)‐ und Iridium(III)‐Komplexe mit Schiff‐Basen aus Salicylaldehyd und α‐Aminosäureestern [1]

Chiral Half‐sandwich Pentamethylcyclopentadienyl Rhodium(III) and Iridium(III) Complexes with Schiff Bases from Salicylaldehyde and α‐Amino Acid Esters [1] A series of diastereoisomeric half‐sandwich complexes with Schiff bases from salicylaldehyde and L‐α‐amino acid esters including chiral metal atoms, [(η⁵‐C₅H₅)(Cl)M(N,O‐Schiff base)], has been obtained from chloro bridged complexes [(η⁵‐C₅Me₅)(Cl)M(μ‐Cl)]₂ (M = Rh, Ir). Abstraction of chloride from these complexes with Ag[BF₄] or Ag[SO₃CF₃] affords the highly sensitive compounds [(η⁵‐C₅Me₅)M(N,O‐Schiff base]⁺X^? (M = Rh, Ir; X = BF₄, CF₃SO₃) to which PPh₃ can be added under formation of [(η⁵‐C₅Me₅)M(PPh₃)(N,O‐Schiff base)]⁺X^?. The diastereoisomeric ratio of the complexes ( 1 ‐ 7 and 11 ‐ 12 ) has been determined from NMR spectra.     

meso‐5,5,7,12,12,14‐Hexa­methyl‐4,11‐di­aza‐1,8‐diazo­nia­cyclo­tetra­decane (S)‐malate(2–) methanol disolvate: a chain of rings generated by two pairs of N—H⃛O hydrogen bonds

The title compound is a methanol‐solvated salt, C₁₆H₃₈N₄²⁺·C₄H₄O₅²⁻·2CH₃OH, in which the ionic components are linked into chains by two pairs of N—H⃛O hydrogen bonds [H⃛O = 1.78–2.21 Å, N⃛O = 2.702 (14)–3.094 (8) Å and N—H⃛O = 160–179°]. The methanol mol­ecules are pendent from the chain and are linked to it by O—H⃛O hydrogen bonds [H⃛O = 1.86 and 1.89 Å, O⃛O = 2.691 (9) and 2.708 (16) Å, and O—H⃛O = 168 and 165°].     

A zigzag chain structure in catena‐poly[[[tetra‐μ‐acetamidato‐κ4N:O;κ4O:N‐dirhodium(II,III)]‐μ‐chloro] methanol solvate]

In {[Rh₂(C₂H₄NO)₄Cl]·CH₃OH}_n, the cationic dirhodium complex and bridging chloro ligands form a one‐dimensional zigzag chain, [Rh₂(acam)₄(μ‐Cl)] (Hacam is acetamide). There is a large difference between the two Rh—Cl distances [2.6076 (14) and 2.5027 (14) Å]. Neighboring chains are connected by two N—H⋯O hydrogen bonds per link between the amidate ligands.     

Binuclear dichlorido(η6‐p‐cymene)ruthenium(II) complexes with bis(nicotinate)‐ and bis(isonicotinate)‐polyethylene glycol ester ligands

Neutral binuclear ruthenium complexes 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 of the general formula [{RuCl₂(η⁶‐p‐cym)}₂ μ‐(N^∩N)] (N^∩N = bis(nicotinate)‐ and bis(isonicotinate)‐polyethylene glycol esters: (3‐py)COO(CH₂CH₂O)_nCO(3‐py) and (4‐py)COO(CH₂CH₂O)_nCO(4‐py), n =1–4), as well as mononuclear [RuCl₂(η⁶‐p‐cym)((3‐py)COO(CH₂CH₂OCH₃)‐κN)], complex 9 , were synthesized and characterized using elemental analysis and electrospray ionization high‐resolution mass spectrometry, infrared, ¹H NMR and ¹³C NMR spectroscopies. Stability of the binuclear complexes in the presence of dimethylsulfoxide was studied. Furthermore, formation of a cationic complex containing bridging pyridine‐based bidentate ligand was monitored using ¹H NMR spectroscopy. Ligand precursors, polyethylene glycol esters of nicotinic ( L1 · 2HCl– L4 · 2HCl and L9 · HCl) and isonicotinic acid dihydrochlorides ( L5 · 2HCl– L8 · 2HCl), binuclear ruthenium(II) complexes 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 and mononuclear complex 9 were tested for in vitro cytotoxicity against 518A2 (melanoma), 8505C (anaplastic thyroid cancer), A253 (head and neck tumour), MCF‐7 (breast tumour) and SW480 (colon carcinoma) cell lines. Copyright © 2014 John Wiley & Sons, Ltd.     

Mononuclear nickel(II) and zinc(II) complexes with deprotonated forms of the tripodal hexadentate ligand 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine

In the crystal structures of both title compounds, [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]nickel(II) [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]nickel(II) chloride methanol disolvate, [Ni(C₂₆H_25.5N₃O₃)]₂Cl·2CH₄O, and [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]zinc(II) perchlorate [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]zinc(II) methanol trisolvate, [Zn(C₂₆H₂₅N₃O₃)]ClO₄·[Zn(C₂₆H₂₆N₃O₃)]·3CH₄O, the 3d metal ion is in an approximately octahedral environment composed of three facially coordinated imine N atoms and three phenol O atoms. The two mononuclear units are linked by three phenol–phenolate O—H...O hydrogen bonds to form a dimeric structure. In the Ni compound, the asymmetric unit consists of one mononuclear unit, one‐half of a chloride anion and a methanol solvent molecule. In the O—H...O hydrogen bonds, two H atoms are located near the centre of O...O and one H atom is disordered over two positions. The Ni^II compound is thus formulated as [Ni(H_1.5L)]₂Cl·2CH₃OH [H₃L is 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine]. In the analogous Zn^II compound, the asymmetric unit consists of two crystallographically independent mononuclear units, one perchlorate anion and three methanol solvent molecules. The mode of hydrogen bonding connecting the two mononuclear units is slightly different, and the formula can be written as [Zn(H₂L)]ClO₄·[Zn(HL)]·3CH₃OH. In both compounds, each mononuclear unit is chiral with either a Δ or a Λ configuration because of the screw coordination arrangement of the achiral tripodal ligand around the 3d metal ion. In the dimeric structure, molecules with Δ–Δ and Λ–Λ pairs co‐exist in the crystal structure to form a racemic crystal. A notable difference is observed between the M—O(phenol) and M—O(phenolate) bond lengths, the former being longer than the latter. In addition, as the ionic radius of the metal ion decreases, the M—O and M—N bond distances decrease.     

Bis[μ‐4‐(ethylammoniomethyl)‐3,5‐dimethylpyrazolato‐κ2N1:N2]bis[(η4‐1,5‐cyclooctadiene)rhodium(I)] dichloride dichloromethane methanol solvate

In the title compound, [Rh₂(C₈H₁₅N₃)₂(C₈H₁₂)₂]Cl₂·CH₂Cl₂·CH₃OH, the dinuclear Rh^I complex has C₂ symmetry and the two pyrazolato ligands act as μ‐bridges. The coordination of each Rh^I cation is completed by one cyclo­octa­diene (COD) ligand. It is shown that the average Rh—C(COD) distance is linearly dependent on the Rh—N(pyrazole) distance in this type of compound, and this is ascribed to the steric hindrance produced by the packing.     

Diimido‐, Imido(oxo)‐, Dioxo‐ und Imido(alkyliden)‐Halbsandwich‐Verbindungen über selektive Hydrolyse und α—H‐Abstraktion an Organylkomplexen des sechswertigen Molybdäns und Wolframs

Diimido, Imido Oxo, Dioxo, and Imido Alkylidene Halfsandwich Compounds via Selective Hydrolysis and α—H Abstraction in Molybdenum(VI) and Tungsten(VI) Organyl Complexes Organometal imides [(η⁵‐C₅R₅)M(NR′)₂Ph] (M = Mo, W, R = H, Me, R′ = Mes, tBu) 4 — 8 can be prepared by reaction of halfsandwich complexes [(η⁵‐C₅R₅)M(NR′)₂Cl] with phenyl lithium in good yields. Starting from phenyl complexes 4 — 8 as well as from previously described methyl compounds [(η⁵‐C₅Me₅)M(NtBu)₂Me] (M = Mo, W), reactions with aqueous HCl lead to imido(oxo) methyl and phenyl complexes [(η⁵‐C₅Me₅)M(NtBu)(O)(R)] M = Mo, R = Me ( 9 ), Ph ( 10 ); M = W, R = Ph ( 11 ) and dioxo complexes [(η⁵‐C₅Me₅)M(O)₂(CH₃)] M = Mo ( 12 ), M = W ( 13 ). Hydrolysis of organometal imides with conservation of M‐C σ and π bonds is in fact an attractive synthetic alternative for the synthesis of organometal oxides with respect to known strategies based on the oxidative decarbonylation of low valent alkyl CO and NO complexes. In a similar manner, protolysis of [(η⁵‐C₅H₅)W(NtBu)₂(CH₃)] and [(η⁵‐C₅Me₅)Mo(NtBu)₂(CH₃)] by HCl gas leads to [(η⁵‐C₅H₅)W(NtBu)Cl₂(CH₃)] 14 und [(η⁵‐C₅Me₅)Mo(NtBu)Cl₂(CH₃)] 15 with conservation of the M‐C bonds. The inert character of the relatively non‐polar M‐C σ bonds with respect to protolysis offers a strategy for the synthesis of methyl chloro complexes not accessible by partial methylation of [(η⁵‐C₅R₅)M(NR′)Cl₃] with MeLi. As pure substances only trimethyl compounds [(η⁵‐C₅R₅)M(NtBu)(CH₃)₃] 16 ‐ 18 , M = Mo, W, R = H, Me, are isolated. Imido(benzylidene) complexes [(η⁵‐C₅Me₅)M(NtBu)(CHPh)(CH₂Ph)] M = Mo ( 19 ), W ( 20 ) are generated by alkylation of [(η⁵‐C₅Me₅)M(NtBu)Cl₃] with PhCH₂MgCl via α‐H abstraction. Based on nmr data a trend of decreasing donor capability of the ligands [NtBu]^2— > [O]^2— > [CHR]^2— ? 2 [CH₃]^— > 2 [Cl]^— emerges.     

Copper(II) and Cadmium(II) Complexes Based on N,N‐Bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine Ligand: Syntheses,Structures, Magnetic,and Luminescent Properties

The reaction of the aryl‐oxide ligand H₂L [H₂L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO₄ · 5H₂O, CuCl₂ · 2H₂O, CuBr₂, CdCl₂ · 2.5H₂O, and Cd(OAc)₂ · 2H₂O, respectively, under hydrothermal conditions gave the complexes [Cu(H₂L¹)₂] · SO₄ · 3CH₃OH ( 1 ), [Cu₂(H₂L²)₂Cl₄] ( 2 ), [Cu₂(H₂L²)₂Br₄] ( 3 ), [Cd₂(HL)₂Cl₂] ( 4 ), and [Cd₂(L)₂(CH₃COOH)₂] · H₂L ( 5 ), where H₂L¹ [H₂L¹ = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H₂L² [H₂L² = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.     

Isomorphous rare‐earth bis[bis(2,6‐diisopropylphenyl)phosphate] complexes and their self‐assembly into two‐dimensional frameworks by intramolecular hydrogen bonds

The crystal structures of rare‐earth diaryl‐ or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]chloridotetrakis(methanol‐κO )neodymium methanol disolvate, [Nd(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (1), and of the lutetium, [Lu(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (2), and yttrium, [Y(C₂₄H₃₄O₄P)Cl(CH₄O)₄]·2CH₃OH, (3), analogues have been obtained by reactions between lithium bis(2,6‐diisopropylphenyl)phosphate and LnCl₃(H₂O)₆ (in a 2:1 ratio) in methanol. Compounds (1)–(3) crystallize in the C 2/c space group. Their crystal structures are isomorphous. The molecule possesses C ₂ symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6‐diisopropylphenyl)phosphate ligands all display a κ¹O‐monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O₂P(O‐2,6‐ⁱPr₂C₆H₃)₂}₂Cl(CH₃OH)₄] molecular unit exhibits two intramolecular O—H…O hydrogen bonds, forming six‐membered rings, and two intramolecular O—H…Cl interactions, forming four‐membered rings. Intermolecular O—H…O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two‐dimensional hydrogen‐bond network. Crystals of bis[bis(2,6‐diisopropylphenyl)phosphato‐κO ]tetrakis(methanol‐κO )(nitrato‐κ²O ,O ′)neodymium methanol disolvate, [Nd(C₂₄H₃₄O₄P)(NO₃)(CH₄O)₄]·2CH₃OH, (4), have been obtained in an analogous manner from NdCl₃(H₂O)₆. Compound (4) also crystalizes in the C 2/c space group. Its crystal structure is similar to those of (1)–(3). The κ²O ,O ′‐bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CN_Nd = 8). Unlike (1)–(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO₃⁻ ligand. The structure of (4) displays intra‐ and intermolecular O—H…O hydrogen bonds similar to those in (1)–(3). Compounds (1)–(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare‐earth complexes.     

Copper(II) Complexes with N‐(9‐anthracenyl)‐N′‐(3‐pyridyl)urea (L) and a Derivative of L: Synthesis,Structure, and Fluorescent Properties

Three copper(II) complexes, [Cu₂(OAc)₄L₂] · 2CH₃OH ( 1 ), [CuBr₂L′₂(CH₃OH)] · CH₃OH ( 2a ), and [CuBr₂L′₂(DMSO)] · 0.5CH₃OH ( 2b ) {L = N‐(9‐anthracenyl)‐N′‐(3‐pyridyl)urea and L′ = N‐[10‐(10‐methoxy‐anthronyl)]‐N′‐(3‐pyridyl)urea} have been synthesized by the reaction of L with the corresponding copper(II) salts. Complex 1 shows a dinuclear structure with a conventional “paddlewheel” motif, in which four acetate units bridge the two Cu^II ions. In complexes 2a and 2b , the anthracenyl ligand L has been converted to an anthronyl derivative L′, and the central metal ion exhibits a distorted square pyramidal arrangement, with two pyridyl nitrogen atoms and two bromide ions defining the basal plane and the apical position is occupied by a solvent molecule (CH₃OH in 2a and DMSO in 2b ).     

A Novel Self‐assembled Nickel(II)‐Cerium(III) Heterotetranuclear Dimer Constructed from N2O2‐type Bisoxime and Terephthalic Acid: Synthesis,Structure, and Photophysical Properties

By self‐assembly of a Salamo‐type ligand H₂L [H₂L = 1,2‐bis(3‐methoxysalicylideneaminooxy)ethane] with Ni(OAc)₂ · 4H₂O, Ce(NO₃)₃ · 6H₂O, and H₂bdc (H₂bdc = terephthalic acid), a novel Ni^II‐Ce^III heterometallic complex, [{Ni(L)Ce(NO₃)₂(CH₃OH)(DMF)}₂(bdc)], was obtained. Two crystallographically equivalent [Ni(L)Ce(NO₃)₂(CH₃OH)(DMF)] moieties lie in the inversion center, and are linked by one bdc^2– ligand leading to a heterotetranuclear dimer, in which the carboxylato group bridges the Ni^II and Ce^III atoms. Moreover, the photophysical properties of the Ni^II‐Ce^III complex were studied.     

3,3′‐Seleno­bis­(propionic acid)

In contrast to Se[CH₂C(O)OH]₂versus S[CH₂C(O)OH]₂, the title compound, Se[CH₂CH₂C(O)OH]₂ or C₆H₁₀O₄Se, is structurally quite similar to its sulfur analogue. The mol­ecule has twofold symmetry. The C—Se—C bond angle is 96.48 (8)° and the Se—C bond lengths are 1.9610 (14) Å. The shortest Se?O intermolecular distance is 3.5410 (11) Å. The O?O distances in the carboxyl­ic acid dimers are 2.684 (2) Å. The temperature dependence of the IR spectrum suggests tautomerism in the solid state.     

Synthesen und Charakterisierungen der ersten Tris‐ und Tetrakis(trifluormethyl)palladate(II) und ‐platinate(II), [M(CF3)3(PPh3)]— und [M(CF3)4]2— (M = Pd,Pt)

Syntheses and Characterizations of the First Tris and Tetrakis(trifluoromethyl) Palladates(II) and Platinates(II), [M(CF₃)₃(PPh₃)]^— and [M(CF₃)₄]^2— (M = Pd, Pt) Tris(trifluoromethyl)(triphenylphosphino)palladate(II) and platinate(II), [M(CF₃)₃PPh₃]^—, and the tetrakis(trifluoromethyl)metallates, [M(CF₃)₄]^2— (M = Pd, Pt), are prepared from the reactions of [MCl₂(PPh₃)₂] and Me₃SiCF₃ / [Me₄N]F or [I(CF₃)₂]^— salts in good yields. [Me₄N][M(CF₃)₃(PPh₃)] crystallize isotypically in the orthorhombic space group Pnma (no. 62) with Z = 4. The NMR spectra of the new compounds are described.     

Monomere und polymere Dimethylaminothioquadratato‐Komplexe: Die Kristallstrukturen von Nickel(II)‐, Cobalt(II)‐, Silber(I)‐, Platin(II)‐, Gold(I)‐, Quecksilber(II)‐ und Blei(II)‐Dimethylaminothioquadrataten

Monomeric and Polymeric Dimethylaminothiosquarato Complexes: The Crystal Structures of Nickel(II), Cobalt(II), Silver(I), Platinum(II), Gold(I), Mercury(II) and Lead(II) Dimethylaminothiosquarates The ligand 2‐dimethylamino‐3, 4‐dioxo‐cyclobut‐1‐en‐thiolate, Me₂N‐C₄O₂S⁻ (L) forms neutral and anionic complexes with nickel(II), cobalt(II)‐, silver(I)‐, platinum(II)‐, gold(I)‐, mercury(II)‐ and lead(II). According to the crystal structures of seven complexes the ligand is O, S‐chelating in [Ni(L)₂(H₂O)₂]·2 H₂O, [Co(L)₂(CH₃OH)₂] and (with limitations) in [Pb(L)₂·DMF]. In the remaining compounds the ligand behaves essentially as a thiolate ligand. The platinum, gold and mercury complexes [TMA]₂[Pt(L)₄], [TMA] [Au(L)₂] and [Hg(L)₂] are monomeric. In [TMA][Ag₂(L)₃]·5.5 H₂O a chain‐like structure was found. In the asymmetric unit of this structure eight silver ions, with mutual distances in the range 2.8949(4) to 3.1660(3)Å, are coordinated by twelve thiosquarato ligands. [Pb(L)₂·DMF] has also a polymeric structure. It contains a core of edge‐bridged, irregular PbS₄ polyhedra. TMA[Au(H₂NC₄O₂S)₂] has also been prepared and its structure elucidated.     

Synthesis and Magnetic Properties of Two New Cobalt Complexes Constructed by Semirigid V‐shaped 5‐(4‐Carboxyphenoxy)‐pyridine‐2‐carboxylic Acid

Two cobalt complexes, [Co₃(L)₂(CH₃OH)₂(μ₃‐OH)₂] ( 1 ) and [Co(L)(bpe)_0.5] · H₂O ( 2 ) [H₂L = 5‐(4‐carboxyphenoxy)‐pyridine‐2‐carboxylic acid; bpe = 1, 2‐bis(4‐pyridyl)ethylene] were synthesized and fully characterized by elemental analyses, IR spectroscopy, single‐crystal X‐ray diffraction, thermogravimetric analysis (TGA), and magnetic analysis. Complex 1 has a two‐dimensional (2D) structure with puckered Co–O–Co chains, and 2 displays a three‐dimensional (3D) network containing one‐dimensional rectangular channels with dimensions of 9.24 × 13.84 Å. In complex 1 , variable‐temperature magnetic susceptibility measurements indicate antiferromagnetic interactions between cobalt magnetic centers.     

[Bis(2‐diphenylphosphinoethyl) sulfide‐κ3P,S,P′](triphenylphosphine‐κP)platinum(II) diperchlorate acetone solvate

In the title compound, [Pt(C₁₈H₁₅P)(C₂₈H₂₈P₂S)]­(ClO₄)₂·­C₃H₆O or [Pt(PPh₃)(PSP)](ClO₄)₂·CH₃COCH₃, where PSP is the potentially tridentate chelate ligand bis(2‐di­phenyl­phosphinoethyl) sulfide, all three donor groups of the PSP ligand are coordinated to the central Pt atom, with Pt—P = 2.310 (1) Å and Pt—S = 2.343 (1) Å. The fourth coordination site is occupied by the P donor of the tri­phenyl­phosphine ligand [Pt—P = 2.289 (1) Å]. The complex cation has exact mirror symmetry, with the S atom, the Pt atom and the P atom of the PPh₃ ligand in the mirror plane. The Pt atom has a distorted square‐planar coordination geometry. A π–π interaction is present between the phenyl rings of the PPh₃ ligand and the terminal –PPh₂ group of the PSP chelate.     

Ligandverhalten von P‐funktionellen Organozinnhalogeniden: Nickel(II)‐, Palladium(II)‐ und Platin(II)‐halogenid‐Komplexe mit Me2(Cl)SnCH2CH2PPh2

Ligand Behaviour of P‐functional Organotin Halides: Nickel(II), Palladium(II), and Platinum(II) Complexes with Me₂(Cl)SnCH₂CH₂PPh₂ Me₂(Cl)SnCH₂CH₂PPh₂ ( 1 ) reacts with Ni^II, Pd^II, and Pt^II halides in molar ratio 2 : 1 forming the complexes [MX₂{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] (M = Ni, Pd, Pt; X = Cl, Br) ( 3 – 6 , 9 , 10 ) ( 7 , 8 : M = Ni; Br instead of Cl). The nickel complexes were isolated and characterized both as the planar ( 3 , 5 , 7 ) and the tetrahedral ( 4 , 6 , 8 ) isomer. Crystal structure analyses and NMR data indicate for the planar nickel complexes 3 , 5 , 7 and [MCl₂{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] ( 9 : M = Pd; 10 : M = Pt) the existence of intra and intermolecular M–Hal…Sn bridges. In a ligand : metal molar ratio of 3 : 1 the complexes [M^éCl{PPh₂CH₂CH₂Sn^⊖Cl₂Me₂}{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] ( 11 : M = Pd; 12 : M = Pt) are formed which represent intramolecular ion pairs. By dehalogenation of [PdCl₂{PPh₂CH₂CH₂Sn(Cl)Me₂}₂] ( 9 ) with sodium amalgam and graphite potassium (C₈K), respectively, the palladacycles cis‐[Pd{PPh₂CH₂CH₂SnMe₂}₂] ( 13 ) and trans‐[Pd(Cl)PPh₂CH₂CH₂SnMe₂{PPh₂CH₂CH₂Sn(Cl)Me₂}] ( 14 ) are formed. From the compounds 1 , 3 , 9 , 11 , and 12 the crystal structures are determined. All compounds are characterized by ¹H, ³¹P, and ¹¹⁹Sn NMR spectroscopy.     

Darstellung und Struktur der Komplexverbindungen trans‐[CoIII(py)4F2][H2F3] und [Pd(py)4]F2 · 1,5 HF · 2 H2O

Synthesis and Crystal Structures of the Complexes trans ‐[Co^III(py)₄F₂][H₂F₃] and [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O The cobalt complex trans‐[Co(III)(py)₄F₂][H₂F₃] ( 1 ) has been prepared by electrochemical oxidation of CoF₂ in a pyridine/HF mixture and the palladium complex [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O ( 2 ) has been obtained via halogen exchange between Pd(py)₂Cl₂ and AgF₂ in pyridine. 1 and 2 crystallize in the space group C2/c with a = 27.928(14), b = 9.019(3), c = 18.335(8) Å, β = 113.41(3)° for 1 and a = 28.183(9), b = 9.399(3), c = 17.397(6) Å, β = 104.66(3)° for 2 , respectively. Concerning the shape and location of the M(py)₄ fragments 1 and 2 are isostructural. The metal atoms occupy special positions in their unit cells with the result that four complex atoms have C₂ symmetry and four complex cations have C_i symmetry giving a total of Z = 8. In 1 two F^– ions complete an octahedral coordination around the Co atoms (Co–F 1.820(2) to 1.834(3) Å). In 2 the shortest Pd–F distance is 3.031(2) Å. This precludes the existence of Pd–F bonds. In 1 one can identify H₂F₃^– groups. In 2 there are larger aggregates, consisting of F^–, HF, and H₂O subunits, connected by H‐bridges. In spite of these differences, both complexes belong to the same type of structure, which may be of a common type M^x+(py)₄F_x · y HF · z H₂O.     

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).