Selenium(IV) fluoride and oxofluoride anions

The [((C₆H₅)₃P)₂N]⁺, [(C₆H₅)₄P]⁺ and [N(CH₃)₄]⁺ salts of SeF₅⁻, SeF₆²⁻ and SeOF₃⁻ and CsSeO₂F were prepared and characterized. Crystal structures were obtained for [((C₆H₅)₃P)₂N][SeF₅] and [((C₆H₅)₃P)₂N][SeOF₃] CH₂Cl₂. In contrast to oxygen-bridged dimeric TeOF₃⁻, the SeOF₃⁻ anion in [((C₆H₅)₃P)₂N][SeOF₃] CH₂Cl₂ is monomeric and represents the first experimentally well determined molecular structure of a monomeric trifluoro-chalcogenite anion. Similarly, [((C₆H₅)₃P)₂N][SeF₅] represents the first example of a structure containing a well-isolated undistorted SeF₅⁻ anion. The NMR and the vibrational spectra and their assignments were re-examined and corrected by comparison with high-level theoretical calculations. Whereas the previously published normal coordinate analysis of SeF₅⁻ is correct, that for SeOF₃⁻ needs major revision.     

Tuning the Magnetic Moment of [Ru2(DPhF)3(O2CMe)L]+ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

The magnetic behaviour of the compounds containing the [Ru₂(DPhF)₃(O₂CMe)]⁺ ion (DPhF^?=N,N′‐diphenylformamidinate) shows a strong dependence on the nature of the ligand bonded to the axial position. The new complexes [Ru₂(DPhF)₃(O₂CMe)(OPMe₃)][BF₄]?0.5 CH₂Cl₂ ( 1 ? 0.5 CH₂Cl₂) and [Ru₂(DPhF)₃(O₂CMe)(4‐pic)][BF₄] ( 2 ) (4‐pic=4‐methylpyridine) clearly display this influence. Complex 1 ?0.5 CH₂Cl₂ shows a magnetic moment corresponding to a S=3/2 system affected by the common zero‐field splitting (ZFS) and a weak antiferromagnetic interaction, whereas complex 2 displays an intermediate behaviour between S=3/2 and S=1/2 systems. The experimental data of complex 1 are fitted with a model that considers the ZFS effect using the Hamiltonian ?_D= S ? D ? S . The weak antiferromagnetic coupling is introduced as a perturbation, using the molecular field approximation. DFT calculations demonstrate that, in the [Ru₂(O₂CMe)(DPhF)₃(L)]⁺ complexes, the energy level of the metal–metal molecular orbitals is strongly dependent on the nature of the axial ligand (L). This study reveals that the increase in the π‐acceptor character of L leads to a greater split between the π* and δ* HOMO orbitals. The influence of the axial ligand in the relative energy between the doublet and quartet states in this type of complexes was also analysed. This study was performed on the new complexes 1 ?0.5 CH₂Cl₂ and 2 . The previously isolated [Ru₂(DPhF)₃(O₂CMe)(OH₂)][BF₄]?0.5 CH₂Cl₂ ( 3 ? 0.5 CH₂Cl₂) and [Ru₂(DPhF)₃(O₂CMe)(CO)][BF₄]?CH₂Cl₂ ( 4 ?CH₂Cl₂) complexes were also included in this study as representative examples of spin‐admixed and low‐spin configurations, respectively. The [Ru₂(DPhF)₃(O₂CMe)]⁺ ( 5 ) unit was used as a reference compound. These theoretical studies are in accordance with the different magnetic behaviour experimentally observed.     

Manganese(II) complexes of hydrazone based NNO-donor ligands and their catalytic activity in the oxidation of olefins

The reaction between tridentate NNO donor hydrazone ligands, (E)-2-cyano-N′-(phenyl(pyridin-2-yl)methylene)acetohydrazide (HL¹) and (E)-2-cyano-N′-(1-(pyridin-2-yl)ethylidene)acetohydrazide (HL²), with MnCl₂·4H₂O in methanol resulted in [Mn(HL¹)Cl₂(CH₃OH)] (1) and [Mn(HL²)Cl₂(CH₃OH)] (2). Molecular structures of the complexes were determined by single-crystal X-ray diffraction. All of the investigated compounds were further characterized by elemental analysis, FT-IR, TGA, and UV–Vis spectroscopy. These complexes were used as catalysts for olefin oxidation in the presence of tert-butylhydroperoxide (TBHP) as an oxidant. Under similar experimental conditions with equal manganese loading, the presence of [Mn(HL²)Cl₂(CH₃OH)] (2) resulted in higher conversion than [Mn(HL¹)Cl₂(CH₃OH)] (1).     

Chemistry of N,N-Dimethylaminoalkylchalcogenolate Complexes of Palladium(II) and Platinum(II)

Abstract

Four different series of N,N-dimethylaminoalkylchalcogenolates, viz. Me₂NCH₂ CH₂E^?, Me₂NCH(Me)CH₂E^?, Me₂NCH₂CH(Me)E^?, and Me₂NCH₂CH₂CH₂E^? (E = S, Se, Te), (referred as E^∩N) have been synthesized and characterized. Their reactions with palladium(II) and platinum(II) precursors have been explored. Complexes of the general formula, [MCl(E^∩N)]_n, [MCl(E^∩N)₂]_n, [MCl(E^∩N)(PR₃)], [M₂Cl₂(μ-E^∩N)₂(PR₃)₂], [M₂(μ-E^∩N)₂(P^∩P)₂]²⁺, etc. have been isolated. All the complexes have been characterized by elemental analysis, IR, NMR (¹H, ¹³C, ³¹P, ⁷⁷Se, ¹²⁵Te, ¹⁹⁵Pt), UV-vis, and FAB mass spectral data. A weak absorption in the electronic spectra of [MCl(E^∩N)(PR₃)] has been attributed to metal mediated ligand-to-ligand charge transfer and showed pronounced chalcogen dependence being red shifted on moving from S → Se → Te. Structures of several complexes have been established by X-ray diffraction analyses. Thermal behavior of some of these complexes has been investigated by TGA.     

Liquid-liquid extraction of metal ions with tris (2,6-dimethoxyphenyl) phosphine and its quaternary phosphonium salts

The extraction of various metal ions from hydrochloric acid solutions with tris(2,6-dimethoxyphenyl)phosphine, [2,6-(MeO)₂C₆H₃]₃P, abbreviated to (2,6-MeOPh)₃P, and its tertiary and quaternary phosphonium salts were studied. A series of phosphonium salts, [(2,6-MeOPh)₃PH]⁺ClO^?₄, [(2,6-MeOPh)₃PR]⁺Br^? and {[(2,6-MeOPh)₃P]₂R′}²⁺ (Br^?)₂, where R = C₁₂H₂₅, C₁₈H₃₇ or C₆H₅CH₂ and R′ = p-CH₂C₆H₄CH₂, (CH₂)₃ and (CH₂)₁₀, were synthesized and applied to an anion exchanger for chloro complex anions of various metal ions. (2,6-MeOPh)₃P and [(2,6-MeOPh)₃PR]⁺Br^? were found to be effective for the extraction of metal ions such as iron(III), gold(III) and gallium(III), forming tetrachloro complex anions of the M^IIICl^?₄ type. The extractabilities of the doubly charged cationic quaternary phosphonium salts [{(2,6-MeOPh)₃P}₂R′]²⁺ (Br^?₂, were found to be superior to those of the singly charged cationic phosphonium salts for metal ions such as cadmium(II), platinum(II) and palladium(II), forming a tetrachloro complex doubly charged aion of the M^IICl^2?₄ type. Most of the metal ions are extracted through ion-pair formation between their chloro complex anions and the phosphonium cations.     

Synthesis,crystal structure and catalytic performance of bis (imino)pyridyl nickel complexes

Two new Ni(II) complexes of 2,6-bis[1-(2,6-diethylphenylimino)ethyl]pyridine (L¹), 2,6-bis[1-(4-methylphenylimino)ethyl]pyridine (L² ) have been synthesized and structurally characterized. Complex Ni(L¹)Cl₂?·?CH₃CN (1), exhibits a distorted trigonal bipyramidal geometry, whereas complex Ni(L¹)(CH₃CN)Cl₂ (2), is six-coordinate with a geometry that can best be described as distorted octahedral. The catalytic activities of complexes 1, 2, Ni{2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine} Cl₂?·?CH₃CN (3), and Ni{2,6-bis[1-(2,6-dimethylphenylimino) ethyl]pyridine}Cl₂?·?CH₃CN (4), for ethylene polymerization were studied under activation with MAO.     

Reaction of tris(2-hydroxyethyl)amine hydrochloride with zinc diacetate and bis(2-methylphenoxy)acetate

Reaction of tris(2-hydroxyethyl)amine hydrochloride Cl⁻ N⁺H(CH₂CH₂OH)₃ with zinc diacetate and bis(2-methylphenoxy)acetate in the molar ratio 2: 1 results in complexes 2[Cl⁻ N⁺H(CH₂CH₂OH)₃]^· Zn (OCOR)₂ (I, II) R= Me (I), 2-MeC₆H₄OCH₂ (II), which contain two protatrane cations linked with zinc diacylate by two coordination bonds HO → Zn. Complexes I and II are also formed by the reaction of the corresponding tris(2-hydroxyethyl)amine hydrochloride acylate RCOO⁻N⁺H(CH₂CH₂OH)₃ with ZnCl₂. The structure of complexes I, II is proved by elemental analysis, IR and ¹H, ¹³C, ¹⁵N NMR spectroscopy.     

Complex Formation of PdII Ion with the Tripodal Ligand Tris[2-(dimethylamino)ethyl]amine

The complex formation of Pd^II with tris[2-(dimethylamino)ethyl]amine (N(CH₂CH₂N(CH₃)₂)₃, Me₆tren) was investigated at 25° and ionic strength I = 1, using UV/VIS, potentiometric, and NMR measurements. Chloride, bromide, and thiocyanate were used as auxiliary ligands. The stability constant of [Pd(Me₆tren)]²⁺ in various ionic media was obtained: log β([Pd(Me₆tren)] = 30.5 (I = 1(NaCl)) and 30.8 (I = 1(NaBr)), as well as the formation constants of the mixed complexes [Pd(HMe₆tren)X]²⁺ from [Pd(HMe₆tren)(H₂O)]³⁺:log K = 3.50 = Cl^?) and 3.64 (X^? = Br^?) and [Pd(Me₆tren)X]⁺ from [Pd(Me₆tren)(H₂O)]²⁺: log K = 2.6 (X^? = Cl^?), 2.8(Br^?) and 5.57 (SCN^?) at I = 1 (NaClO₃). The above data, as well as the NMR measurements do not provide any evidence for the penta-coordination of Pd^II, proposed in some papers.     

A comparative theoretical study of the reactivities of the Al+ and Cu+ ions toward methylamine and dimethylamine

A very recent laser ablation‐molecular beam experiment shows that an Al⁺ ion can react with a single methylamine (MA, CH₃NH₂) or dimethylamine (DMA, (CH₃)₂NH) molecule to form a 1:1 ion–molecule complex Al⁺[CH₃NH₂] or Al⁺[(CH₃)₂NH)], whereas a dehydrogenated complex ion Cu⁺[CH₃N] or Cu⁺[C₂H₅N] is detected, respectively, in the similar reaction for a Cu⁺ ion. Here, we show a comparative density functional theory study for the reactivities of the Al⁺ and Cu⁺ ions toward MA and DMA to reveal the intrinsic mechanism. It is found that the interactions of the Al⁺ ion with MA and DMA are mostly electrostatic, leading to the direct ion–molecule complexes, Al⁺? NH₂CH₃ and Al⁺? NH( CH₃)₂, in contrast to the non‐negligible covalent character in the corresponding Cu⁺‐containing complexes, Cu⁺? NH₂CH₃ and Cu⁺? NH( CH₃)₂. The general dehydrogenation mechanism for MA and DMA promoted by the Cu⁺ ion has been shown, and the preponderant structures contributing to the mass spectra of the product ions Cu⁺[CH₃N] and Cu⁺[C₂H₅N] are rationalized as Cu⁺? NHCH₂ and Cu⁺? N( CH₂)( CH₃). The presumed dehydrogenation reactions are also discussed for the Al⁺‐containing systems. However, the involved barriers are found to be too high to be overcome at low energy conditions. These results have rationalized all the experimental observations well. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Dissociative photoionization of Al2(Ch3)6 and Al2(Ch3)3Cl3 in the range 40–100 eV

Dissociation processes of the organoaluminum compounds Al₂(CH₃)₆ and Al₂(CH₃)₃Cl₃ have been studied in the range of valence and Al:2p core-level ionization by means of photoelectron–photoion and photoion–photoion coincidence techniques. The double-ionization threshold and the Al:2p core-ionization threshold of Al₂(CH₃)₆ are estimated to be about 30 and 80 eV

1 1 eV = 96.4853 kJ mol^?1.

respectively. The relative yields of the H⁺?Al⁺ and H⁺?CH_m,⁺ (m′ = 0–3) ion pairs are enhanced around the Al:2p core-ionization threshold of Al₂(CH₃)₆. The photoion–photoion coincidence intensities of Al₂(CH₃)₃Cl₃ are negligibly small throughout the energy range studied. The ratio of the relative yield of AlC₂H₆⁺ to that of Al⁺ increases smoothly through the Al:2p core-ionization and/or excitation region of Al₂(CH₃)₃Cl₃. The variation of the fragmentation pattern with photon energy is discussed in conjunction with the relevant electronic states.     

Synthesis,Structures and Spectroscopic Properties of Platinum(II), Palladium(II) and Copper(I) Halide Complexes with Pyrimidine‐phosphine Ligand

The reactions of pyrimidine‐phosphine ligand N‐[(diphenylphosphino)methyl]‐2‐pyrimidinamine ( L ) with various metal salts of Pt^II, Pd^II and Cu^I provide three new halide metal complexes, Pt₂Cl₄(μ‐L)₂·2CH₂Cl₂ ( 1 ), Pd₂Cl₄(μ‐L)₂ ( 2 ), and [Cu₂(μ‐I)₂L₂]_n ( 3 ). Single crystal X‐ray diffraction studies show that complexes 1 and 2 display a similar bimetallic twelve‐membered ring structure, while complex 3 consists of one‐dimensional polymeric chains, which are further connected into a 2‐D supramolecular framework through hydrogen bonds. In the binuclear complexes 1 and 2 , the ligand L serves as a bridge with the N and P as coordination atoms, but in the polymeric complex 3 , both bridging and chelating modes are adopted by the ligand. The spectroscopic properties of complexes 1 ‐ 3 as well as L have been investigated, in which complex 3 exhibits intense photoluminescence originating from intraligand charge transfer (ILCT) π→π* and metal‐to‐ligand charge‐transfer (MLCT) excited states both in acetonitrile solution and solid state, respectively.     

Synthetic,spectral as well as in vitro antimicrobial studies on some bismuth(III) bis(N,N‐dialkyldithiocarbamato) alkylenedithiophosphates

Mixed sulfur donor ligand complexes of the type bismuth(III) bis(N,N‐dialkyldithiocarbamato) alkylenedithiophosphate, [R₂NCS₂]₂BiS₂POGO [where R = CH₃ and C₂H₅; G = ‐CH₂‐C(C₂H₅)₂‐CH₂‐, ‐CH₂‐C(CH₃)₂‐CH₂‐, ‐CH(CH₃)‐CH(CH₃)‐ and ‐C(CH₃)₂‐C(CH₃)₂‐] were synthesized in 1:1 molar ratio of bismuth(III) bis(N,N‐dialkyldithiocarbamate) chloride and ammonium alkylenedithiophosphate in refluxing benzene and characterized by melting point, molecular weight determinations, elemental analysis (C, H, N, Bi and S) and spectral [UV, IR,NMR (¹H,¹³C and ³¹P) and powder X ray diffraction] studies; all these studies were in good agreement with the synthesized complexes. These newly synthesized derivatives are yellow and brown colored solids and are soluble in common organic solvents like benzene, chloroform, dichloromethane and DMF. Based on the physicochemical and spectral studies, a tentative structure of these newly synthesized complexes was assigned and the average particle size of the synthesized complexes determined by powder XRD, showing that nano range polycrystalline particles were formed with a monoclinic crystal system. These complexes were also screened for their antimicrobial activities using the well diffusion method. The free ligands as well as their mixed metal complexes were tested in vitro against four bacterial strains: two Gram‐positive, Staphylococcus aureus (ATCC 9144) (G⁺) and Bacillus subtilis (ATCC 6051), (G⁺) and two Gram‐negative, Escherichia coli (ATCC 9637) (G^?) and Pseudomonas aeruginosa (ATCC 25619) (G^?) to assess their antimicrobial properties. The results were indeed positive and exhibited good antibacterial effects. Chloroamphenicol used as a standard for comparison and synthesized complexes showed good antibacterial effects over chloroamphenicol. On the basis of these studies, the synthesized complexes help to understand the different structural and biological properties of main group elements with sulfur donor ligands. Copyright © 2010 John Wiley & Sons, Ltd.     

Kraftkonstanten von Verbindungen des Typs (CH3)3ElCl+X− (El = N,P, As,Sb; X− = SbCl6−)

Force Constants of Compounds of the Type (CH₃)₃ElCl⁺X^?(El = N, P, As, Sb; X^? = SbCl₆^?) For the cations (CH₃)₃NCl⁺ ( 1 ), (CH₃)₃PCl⁺ ( 2 ), (CH₃)₃AsCl⁺ ( 3 ), and (CH₃)₃SbCl⁺ ( 4 ) a normal coordinate analysis using a general valence force field is performed by the method of Fadini. The force constants are discussed. Calculations of the potential energy distribution show, that the skeletal vibrations in 4 are all characteristic vibrations, but there is a strong coupling of vibrations in 1 .     

Darstellung von Trifluormethylhalogen-Iodaten(I) des Typs (CH3)4N+CF3IX− (X = F,Cl, Br) und Trifluormethyltrifluormethoxyiodat(I) (CH3)4N+CF3IOCF3−

Preparation of Trifluormethylhalogen Iodate(I) Salts (CH₃)₄N⁺CF₃IX^? (X = F, Cl, Br) and Trifluormethyltrifluormethoxy Iodate(I) (CH₃)₄N⁺CF₃IOCF₃^? We describe the preparation of new trifluormethyliodate(I) salts CF₃IX^? (X = F, Cl, Br, OCF₃). (CH₃)₄N⁺CF₃ICl^? and (CH₃)₄N⁺CF₃IBr^? are obtained via addition of CF₃I with the corresponded tetramethylammonium halogenide. (CH₃)₄N⁺CF₃IOCF₃^? is synthesized by comproportionation of (CH₃)₄N⁺CF₃ICl^? with CF₃OCl under formation of Cl₂ at ?78°C. (CH₃)₄N⁺CF₃IF^? is formed either, through thermolysis of (CH₃)₄N⁺ CF₃IOCF₃^? under separation of COF₂, or reaction of CF₃I with (CH₃)₄N⁺ OCF₃^?. The thermolabile compounds have been characterized by i.r., Raman, ¹⁹F-, ¹³C NMR spectroscopy.     

[N⋅⋅⋅I+⋅⋅⋅N] Halogen‐Bonded Dimeric Capsules from Tetrakis(3‐pyridyl)ethylene Cavitands

Two [N???I⁺???N] halogen‐bonded dimeric capsules using tetrakis(3‐pyridyl)ethylene cavitands with different lower rim alkyl chains are synthesized and analyzed in solution and the gas phase. These first examples of symmetrical dimeric capsules making use of the iodonium ion (I⁺) as the main connecting module are characterized by ¹H NMR spectroscopy, diffusion ordered NMR spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI‐MS), and ion mobility‐mass spectrometry (TW‐IMS) experiments. The synthesis and effective halogen‐bonded dimerization proceeds through analogous dimeric capsules with [N???Ag⁺???N] binding motifs as the intermediates as evidenced by the X‐ray structures of (CH₂Cl₂)₂@[ 3 a ₂?Ag₄?(H₂O)₂?OTs₄] and (CH₂Cl₂)₂@[ 3 a ₂?Ag₄?(H₂O)₄?OTs₄], two structurally different capsules.     

Uncatalyzed and ruthenium(III)‐catalyzed reaction of acidic chlorite with methylene violet

The kinetics and mechanism of the uncatalyzed and Ru(III)‐catalyzed oxidation of methylene violet (3‐amino‐7‐diethylamino‐5‐phenyl phenazinium chloride) (MV⁺) by acidic chlorite is reported. With excess concentrations of other reactants, both uncatalyzed and catalyzed reactions had pseudo‐first‐order kinetics with respect to MV⁺. The uncatalyzed reaction had first‐order dependence on chlorite and H⁺ concentrations, but the catalyzed reaction had first‐order dependence on both chlorite and catalyst, and a fractional order with respect to [H⁺]. The rate coefficient of the uncatalyzed reaction is (5.72 ± 0.19) M^?2 s^?1, while the catalytic constant for the catalyzed reaction is (22.4 ± 0.3) × 10³ M^?1 s^?1. The basic stoichiometric equation is as follows: 2MV⁺ + 7ClO₂^? + 2H⁺ = 2P + CH₃COOH + 4ClO₂ + 3Cl^?, where P⁺ = 3‐amino‐7‐ethylamino‐5‐phenyl phenazinium‐10‐N‐oxide. Stoichiometry is dependent on the initial concentration of chlorite present. Consistent with the experimental results, pertinent mechanisms are proposed. The proposed 15‐step mechanism is simulated using literature; experimental and estimated rate coefficients and the simulated plots agreed well with the experimental curves. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 294–303, 2003     

Synthetic,spectral, thermal and antimicrobial studies on some bis(N,N′‐dialkyldithiocarbamato) antimony(III) alkylenedithiophosphates

Bis(N, N′‐dialkyldithiocarbamato)antimony(III) alkylenedithiophosphates of the type [R₂NCS₂]₂ SbS(S)POGO [where NR₂ = N(CH₃)₂, N(C₂H₅)₂ and N(CH₂)₄; G = ? CH₂? C(C₂H₅)₂? CH₂? , ? CH₂? C(CH₃)₂? CH₂? , ? CH(CH₃)? CH(CH₃)? and ? C(CH₃)₂? C(CH₃)₂? ] were synthesized and characterized by physico‐chemical, spectral [UV, IR and NMR (¹H, ¹³C and ³¹P)] and thermal (TG, DTA and DSC) analysis. The TG decomposition analysis step of the complex indicated the formation of Sb₂S₃ as the final product. The first endothermic peak in DSC indicated the melting point of the complexes. These complexes were screened for their antimicrobial activities using the disk diffusion method. All the complexes showed good activity as antibacterial and antifungal agents on some selected bacterial and fungal strains, which increased on increasing the concentration. Chloroamphenicol and terbinafin were used as standards for comparison. Copyright © 2007 John Wiley & Sons, Ltd.     

Palladium(II)‐ und Platin(II)‐Komplexe mit dem Antimalariamittel Mefloquin als Liganden

Metal Complexes of Biologically Important Ligands. CXXVI. Palladium(II) and Platinum(II) Complexes with the Antimalarial Drug Mefloquine as Ligand The coordination sites of the antimalarial drug mefloquine (L) were studied. Reactions of the chloro bridged complexes (allyl)Pd(μ‐Cl)₂Pd(allyl) and (R₃P)(Cl)M(μ‐Cl)₂M(Cl)(PR₃) (M = Pd, Pt) with racemic mefloquine give the compounds (allyl)(Cl)Pd(L) ( 1 ), Cl₂(Et₃P)Pt(L) ( 2 ) and Cl₂(Et₃P)Pd(L) ( 3 ) with coordination of the piperidine N atom of mefloquine. In the presence of NaOMe the N,O‐chelate complexes Cl(Et₃P)Pt(L–H⁺) ( 4 ) and Cl(R₃P)Pd(L–H⁺) ( 5 , 6 , R = Et, nBu) were obtained. Protection of the piperidine N atom of mefloquine by protonation allows the synthesis of the complexes Cl₂(Et₃P)Pt(L + H⁺) ( 7 ) in which mefloquine is coordinated via the quinoline N atom. The structures of 2 , 3 and 4 were determined by X‐ray diffraction analysis. In the crystal of 4 pairs of enantiomers are found which are linked by two hydrogen bridges between the amine group and the chloro ligand.     

Darstellung und Eigenschaften von Diphthalocyaninaten des Bismuts, [Bi(Pc)2]k (k = 1−, 0, 1+); Kristallstruktur von gemischtvalentem [Bi(Pc)2] · CH2Cl2

Synthesis and Properties of Diphthalocyaninates of Bismuth, [Bi(Pc)₂]^k (k = 1?, 0, 1+); Crystal Structure of mixed-valent [Bi(Pc)₂] · CH₂Cl₂ Blue di(phthalocyaninato(2-))bismuthate(III), [Bi(Pc^2?)₂]^?, is obtained by the reaction of BiO(NO₃) with molten 1,2-dicyanobenzene in the presence of potassium methylate and isolated as tetra-n-butylammonium (ⁿBu₄N)⁺ and bis(triphenylphosphine)iminium (PNP)⁺ salt. Green mixed-valent [Bi(Pc)₂] · CH₂Cl₂ is prepared by anodic oxidation of [Bi(Pc^2?)₂]^?. It crystallizes in the orthorhombic γ modification (Pnma; a = 28.176(5), b = 22.913(3), c = 7.925(1) Å, Z = 4). The Bi^III ion is eightfold coordinated by the N_iso atoms of the slightly distorted Pc ligands in a square antiprismatic manner. The average Bi? N_iso bond distance is 2.467 Å. The complex is paramagnetic (μ_eff = 1.84 μ_B). Oxidation of [Bi(Pc^2?)₂]^? with bromine yields purple, diamagnetic [Bi(Pc^?)₂]Br_x (1.5 ≤ x ≤ 2.5). The redox properties are investigated electrochemically. UV-Vis-NIR, MIR/FIR and resonance Raman spectra of the new bismuth(III) complexes are discussed and compared with those of diphthalocyaninates of the lanthanides.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.