Stibinidene and Bismuthinidene as Two‐Electron Donors for Transition Metals (Co and Mn)

The reaction of stibinidene and bismuthinidene ArM [where Ar=C₆H₃‐2,6‐(CH=NtBu)₂; M=Sb ( 1 ), Bi ( 2 )] with transition metal (TM) carbonyls Co₂(CO)₈ and Mn₂(CO)₁₀ produced unprecedented ionic complexes [(ArM)₂Co(CO)₃]⁺[Co(CO)₄]^? and [(ArM)₂Mn(CO)₄]⁺[Mn(CO)₅]^? [where M=Sb ( 3 , 5 ), Bi ( 4 , 6 )]. The pnictinidenes 1 and 2 behaved as two‐electron donors in this set of compounds. Besides the M→TM bonds, the topological analysis also revealed a number of secondary interactions contributing to the stabilization of cationic parts of titled complexes.     

Mono‐ and Dinuclear Heteroleptic Cobalt Complexes with α‐Diimine and Polyarene Ligands

Reactions of the dimeric cobalt complex [(L^?Co)₂] ( 1 , L=[(2,6‐iPr₂C₆H₃)NC(Me)]₂) with polyarenes afforded a series of mononuclear and dinuclear complexes: [LCo(η⁴‐anthracene)] ( 2 ), [LCo(μ‐η⁴:η⁴‐naphthalene)CoL] ( 3 ), and [LCo(μ‐η⁴:η⁴‐phenanthrene)CoL] ( 4 ). The pyrene complexes [{Na₂(Et₂O)₂}{LCo(μ‐η³:η³‐pyrene)CoL}] ( 5 ) and [{Na₂(Et₂O)₃}{LCo(η³‐pyrene)}] ( 6 ) were obtained by treating precursor 1 with pyrene followed by reduction with Na metal. These complexes contain three potential redox active centers: the cobalt metal and both α‐diimine and polyarene ligands. Through a combination of X‐ray crystallography, EPR spectroscopy, magnetic susceptibility measurement, and DFT computations, the electronic configurations of these complexes were studied. It was determined that complexes 2 – 4 have a high‐spin Co^I center coupled with a radical α‐diimine ligand and a neutral polyarene ligand. Whereas, the ligand L in complexes 5 and 6 has been further reduced to the dianion, the cobalt remains in a formal (I) oxidation state, and the pyrene molecule is either neutral or monoanionic.     

Protonated Ethylene Carbonate: A Highly Resonance-Stabilized Cation

Salts containing the monoprotonated ethylene carbonate species of were obtained by reacting it with the superacidic systems XF/MF₅ (X=H, D; M=Sb, As). The salts in terms of [C₃H₅O₃]⁺[SbF₆]⁻, [C₃H₅O₃]⁺[AsF₆]⁻ and [C₃H₄DO₃]⁺[AsF₆]⁻ were characterized by low-temperature infrared and Raman spectroscopy. In order to generate the diprotonated species of ethylene carbonate, an excess of Lewis acid was used. However, this only led to the formation of [C₃H₅O₃]⁺[Sb₂F₁₁]⁻, which was characterized by a single-crystal X-ray structure analysis. Quantum chemical calculations on the B3LYP/aug-cc-PVTZ level of theory were carried out for the [C₃H₅O₃]⁺ cation and the results were compared with the experimental data. A Natural Bond Orbital (NBO) analysis revealed sp² hybridization of each atom belonging to the CO₃ moiety, thus containing a remarkably delocalized 6π-electron system. The delocalization is confirmed by a ¹³C NMR-spectroscopic study of [C₃H₅O₃]⁺[SbF₆]⁻.     

Facile Access to Transition‐Metal–Carbonyl Complexes with an Amidinate‐Stabilized Chlorosilylene Ligand

Three transition‐metal–carbonyl complexes [V( L )(CO)₃(Cp)] ( 1 ), [Co( L )(CO)(Cp)] ( 2 ), and [Co( L₂ )(CO)₃]⁺[CoCO)₄]^? ( 3 ), each containing stable N‐heterocyclic‐chlorosilylene ligands ( L ; L =PhC(NtBu)₂SiCl) were synthesized from [V(CO)₄(Cp)], [Co(CO)₂(Cp)], and Co₂(CO)₈, respectively. Complexes 1 , 2 , 3 were characterized by NMR and IR spectroscopy, EI‐MS spectrometry, and elemental analysis. The molecular structures of compounds 1 , 2 , 3 were determined by single‐crystal X‐ray diffraction.     

An Extremely Porous Hydrogen‐Bonded Framework Composed of d‐Penicillaminato CoIII2AuI3 Complex Anions and Aqua Cobalt(II) Cations: Formation and Stepwise Structural Transformation

A unique example of a hydrogen‐bonded ionic solid with a porosity of 80 %, [Co(H₂O)₆]₃[Co₂Au₃(d ‐pen‐N,S)₆]₂ ( 1 ; d ‐H₂pen=d ‐penicillamine), composed of [Co(H₂O)₆]²⁺ cations and [Co₂Au₃(d ‐pen‐N,S)₆]^3? anions, is reported. Solid 1 was kinetically produced and was then transformed stepwise into two more thermodynamically stable solids with lower porosities, [Co(H₂O)₄][Co(H₂O)₆]₂[Co₂Au₃(d ‐pen‐N,S)₆]₂ ( 2 ) and [Co(H₂O)₄]₃[Co₂Au₃(d ‐pen‐N,S)₆]₂ ( 3 ), through the coordination of the free carboxylate groups in [Co₂Au₃(d ‐pen‐N,S)₆]^3? to Co^II centers. Solids 1 – 3 were structurally characterized, and the selective adsorption of small molecules into their pores was investigated.     

The preparation and x-ray structure of [P(C2H5)4]+[N3]− and the attempted preparation of [PH4]+[N3]−

Tetraethylphosphonium azide, [P(C₂H₅)₄ ]⁺[N₃ ]⁻, was prepared from tetraethyl phosphonium bromide and silver azide. Single crystals of [P(C₂H₅)₄ ]⁺[N₃ ]⁻ were grown from dichloromethane/THF (10:1) solution. The structure was determined by single-crystal X-ray diffraction analysis. [P(C₂H₅)₄ ]⁺[N₃ ]⁻ crystallizes in the monoclinic space group C 2/c with Z = 4 and unit cell dimensions a = 12.961(6), b = 6.835(3), c = 12.378(6) Å, and β = 100.57(4)°. The attempted preparation of phosphonium azide [PH₄]⁺[N₃]⁻ from phosphonium iodide and silver azide lead instead to the formation of PH₃ and HN₃. The instability of [PH₄]⁺[N₃]⁻ with respect to PH₃ and HN₃ is in accord with thermodynamic considerations according to which the reaction PH₃(g) and HN₃(g) to yield [PH₄ ]⁺[N₃ ]⁻ is thermodynamically unfavorable. (Non SI units employed: kcal ≈ 4.184 J, Å = 10⁻¹⁰ m.) © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:129–132, 1998     

Two mononuclear cobalt(III) complexes exhibiting phenoxazinone synthase activity

Two mononuclear cobalt(III) complexes, namely [LCo(tmtp)(H₂O)]ClO₄?MeOH ( 1 ) (tmtp = tri(m‐tolyl)phosphine) and [LCo(PPh₃)(H₂O)]PF₆ ( 2 ), have been prepared from a polydentate ligand, N,N′‐bis(3‐methoxysalicylidehydene)cyclohexane‐1,2‐diamine ( H ₂ L ). Standard analytical techniques such as elemental analysis and UV–visible and Fourier transform infrared spectroscopies were used to characterize both complexes. The solid‐state molecular structures of both complexes were confirmed from single‐crystal X‐ray diffraction analysis. Structural analyses show that the Co(III) ion occupies the centre of a distorted octahedron in a complex cation: [LCo(tmtp)(H₂O)]⁺ and [LCo(PPh₃)(H₂O)]⁺ for 1 and 2 , respectively. Phenoxazinone synthase activities of both complexes were screened. Kinetic studies and other experimental observations reveal that the reaction follows rate saturation kinetics and proceeds through the formation of a catalyst (complex)–substrate adduct. The turnover number (K_cat) of complex 2 is 54.07 h^?1, exhibiting better catalytic activity compared to 1 (K_cat = 45.11 h^?1).     

Magnesium tetraorganyl derivatives of group 13 metals as intermediate products in the synthesis of group 13 metal alkyls and aryls

Reactions of organomagnesium halides with group 13 metal halides lead to the formation of R₃M type compounds (R = alkyl, aryl; M = Al, Ga, In) and are considered as the simplest methods of R₃M compound syntheses. These seemingly simple reactions reveal a much more complex chemistry involving mixed magnesium-group 13 metal compounds. To elucidate the reaction course of reactions of organomagnesium halides with group 13 metal halides, we have studied reactions of R₃M with organomagnesium halides. The interaction of Et₃M with R¹MgX led to the formation of following products being mixtures of crystalline ionic complexes with the general composition of [Et_4-nR¹_nM]⁻[XMg (thf)₅]⁺·(thf): [Et_2.2Al(CH=CH₂)_1.8]⁻[BrMg (thf)₅]⁺·(thf) ( 1 ), [Et₃Ga(CH=CH₂)]⁻[BrMg (thf)₅]⁺·(thf) ( 2 ), [Et₄Al]⁻[BrMg (thf)₅]⁺·(thf) ( 3 ), [Et₄Ga]⁻[BrMg (thf)₅]⁺·(thf) ( 4 ), [Et_2.9Al(C₆H₅)_1.1]⁻[BrMg (thf)₅]⁺·(thf) ( 5 ), [Et_2.9Ga(C₆H₅)_1.1]⁻[BrMg (thf)₅]⁺·(thf) ( 6 ), [Et_3.4GaMe_0.6]⁻[IMg (thf)₅]⁺·(thf) ( 7 ) and [Et₄In]⁻[BrMg (thf)₅]⁺·(thf) ( 8 ). A comparison of the production course of group 13 metal trialkyls R₃M with a thermal decomposition of 1–8 products showed that reactions of MX₃ with RMgX (X = Br, I; R = alkyl, aryl) yield initially intermediate ionic compounds, which must then be thermally decomposed to obtain pure R₃M compounds. If group 13 metal bromides and iodides, and alkyl (aryl)magnesium bromides and iodides in thf are used, only intermediate products with the [R₄M]⁻[XMg (thf)₅]⁺·(thf) structure are formed.     

Six Coordination Polymers based on 4‐(1H‐Imidazol‐1‐yl)phthalic Acid: Structural Diversities,Magnetism and Luminescence Properties

The coordination polymers (CPs), [Ni(L)(H₂O)₄]_n ( 1 ), [Co(HL)₂(H₂O)₂]_n ( 2 ), {[Cu(L)(H₂O)₃] · H₂O}_n ( 3 ), [Mn(L)(H₂O)₂]_n ( 4 ), [Cd(L)(H₂O)₂]_n ( 5 ), and {[Zn₂(L)₂] · H₂O}_n ( 6 ), were solvothermally synthesized by employing the imidazol‐carboxyl bifunctional ligand 4‐(1H‐imidazol‐1‐yl) phthalic acid (H₂L). Single‐crystal X‐ray diffraction indicated that the L^2–/HL^– ligands display various coordination modes with different metal ions in 1 – 6 . Complexes 1 and 2 show one‐dimensional (1D) chain structures, whereas complexes 3 – 6 show 2D layered structures. The magnetic properties of these complexes were investigated. Complexes 1 and 3 indicate weak ferromagnetic interactions, whereas complexes 2 and 4 demonstrate antiferromagnetic interactions. In addition, luminescence properties of 5 and 6 were measured and studied in detail.     

Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe,V. Heteronukleare Co/Rh-, Co/Ir-, Rh/Ir- und Ti/Ir-Komplexe mit dem Bis(cyclopentadienyl)methan-Dianion als Brückenliganden

Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes, V^[1]. – Heteronuclear Co/Rh-, Co/Ir-, Rh/Ir-, and Ti/Ir Complexes with the Bis(cyclopentadienyl)methane Dianion as Bridging Ligand^* The lithium and sodium salts of the [C₅H₅CH₂C₅H₄]^- anion, 1 and 2 , react with [Co(CO)₄I], [Rh(CO)₂Cl]₂, and [Ir(CO)₃Cl]n to give predominantly the mononuclear complexes [(C₅H₅-CH₂C₅H₄)M(CO)₂] ( 3, 5, 7 ) together with small amounts of the dinuclear compounds [CH₂(C₅H₄)₂][M(CO)₂]₂ ( 4, 6, 8 ). The ¹H- and ¹³C-NMR spectra of 3, 5 , and 7 prove that the CH₂C₅H₅ substituent is linked to the π-bonded ring in two isomeric forms. Metalation of 5 and 7 with nBuLi affords the lithiated derivatives 9 and 10 from which on reaction with [Co(CO)₄I], [Rh(CO)₂Cl]₂, and [C₅H₅TiCl₃] the heteronuclear complexes [CH₂(C₅H₄)₂][M(CO)₂][M′(CO)₂] ( 11–13 ) and [CH₂(C₅H₄)₂]-[Ir(CO)₂][C₅H₅TiCl₂] ( 17 ) are obtained. Photolysis of 11 and 12 leads almost quantitatively to the formation of the CO-bridged compounds [CH₂(C₅H₄)₂][M(CO)(μ-CO)M′(CO)] ( 14, 15 ). According to an X-ray crystal structure analysis the Co/Rh complex 14 is isostructural to [CH₂(C₅H₄)₂][Rh₂(CO)₂(μ-CO)] ( 16 ).     

Homo‐ and Heterodinuclear Ir and Rh Imine‐functionalized Protic NHC Complexes: Synthetic,Structural Studies,and Tautomerization/Metallotropism Insights

The influence of the potentially chelating imino group of imine‐functionalized Ir and Rh imidazole complexes on the formation of functionalized protic N‐heterocyclic carbene (pNHC) complexes by tautomerization/metallotropism sequences was investigated. Chloride abstraction in [Ir(cod)Cl{C₃H₃N₂(DippN=CMe)‐κN3}] ( 1 a ) (cod=1,5‐cyclooctadiene, Dipp=2,6‐diisopropylphenyl) with TlPF₆ gave [Ir(cod){C₃H₃N₂(DippN=CMe)‐κ²(C2,N_imine)}]⁺[PF₆]^? ( 3 a ⁺[PF₆]^?). Plausible mechanisms for the tautomerization of complex 1 a to 3 a ⁺[PF₆]^? involving C2?H bond activation either in 1 a or in [Ir(cod){C₃H₃N₂(DippN=CMe)‐κN3}₂]⁺[PF₆]^? ( 6 a ⁺[PF₆]^?) were postulated. Addition of PR₃ to complex 3 a ⁺[PF₆]^? afforded the eighteen‐valence‐electron complexes [Ir(cod)(PR₃){C₃H₃N₂(DippN=CMe)‐κ²(C2,N_imine)}]⁺[PF₆]^? ( 7 a ⁺[PF₆]^? (R=Ph) and 7 b ⁺[PF₆]^? (R=Me)). In contrast to Ir, chloride abstraction from [Rh(cod)Cl{C₃H₃N₂(DippN=CMe)‐κN3}] ( 1 b ) at room temperature afforded [Rh(cod){C₃H₃N₂(DippN=CMe)‐κN3}₂]⁺[PF₆]^? ( 6 b ⁺[PF₆]^?) and [Rh(cod){C₃H₃N₂(DippN=CMe)‐κ²(C2,N_imine)}]⁺[PF₆]^? ( 3 b ⁺[PF₆]^?) (minor); the reaction yielded exclusively the latter product in toluene at 110 °C. Double metallation of the azole ring (at both the C2 and the N3 atom) was also achieved: [Ir₂(cod)₂Cl{μ‐C₃H₂N₂(DippN=CMe)‐κ²(C2,N_imine),κN3}] ( 10 ) and the heterodinuclear complex [IrRh(cod)₂Cl{μ‐C₃H₂N₂(DippN=CMe)‐κ²(C2,N_imine),κN3}] ( 12 ) were fully characterized. The structures of complexes 1 b , 3 b ⁺[PF₆]^?, 6 a ⁺[PF₆]^?, 7 a ⁺[PF₆]^?, [Ir(cod){C₃HN₂(DippN=CMe)(DippN=CH)(Me)‐κ²(N3,N_imine)}]⁺[PF₆]^? ( 9 ⁺[PF₆]^?), 10? Et₂O ? toluene, [Ir₂(CO)₄Cl{μ‐C₃H₂N₂(DippN=CMe)‐κ²(C2,N_imine),κN3}] ( 11 ), and 12? 2 THF were determined by X‐ray diffraction.     

Ring Expansions of Nonpolar Polyphosphorus Rings

The reaction of the phosphinidene complex [Cp*P{W(CO)₅}₂] ( 1 a ) (Cp*=C₅Me₅) with the anionic cyclo-P_n ligand complex [(η³-P₃)Nb(ODipp)₃]⁻ ( 2 , Dipp=2,6-diisopropylphenyl) resulted in the formation of [{W(CO)₅}₂{μ₃,η^3:1:1-P₄Cp*}Nb(ODipp)₃]⁻ ( 3 ), which represents an unprecedented example of a ring expansion of a polyphosphorus-ligand complex initiated by a phosphinidene complex. Furthermore, the reaction of the pnictinidene complexes [Cp*E{W(CO)₅}₂] (E=P: 1 a , As: 1 b ) with the neutral complex [Cp′′′Co(η⁴-P₄)] (Cp′′′=1,2,4-tBu₃C₅H₂) led to a cyclo-P₄E ring (E=P, As) through the insertion of the pentel atom into the cyclo-P₄ ligand. Starting from 1 a , the two isomers [Cp′′′Co(μ₃,η^4:1:1-P₅Cp*){W(CO)₅}₂] ( 5 a , b ), and from 1 b , the three isomers [Cp′′′Co(μ₃,η^4:1:1-AsP₄Cp*){W(CO)₅}₂] ( 6 a – c ) with unprecedented cyclo-P₄E ligands (E=P, As) were isolated. The complexes 6 a – c represent unique examples of ring expansions which lead to new mixed five-membered cyclo-P₄As ligands. The possible reaction pathways for the formation of 5 a , b and 6 a – c were investigated by a combination of temperature-dependent ³¹P{¹H} NMR studies and DFT calculations.     

The reactions of AgI electrophile with [Fe2(η-C5H5)2(CO)2(L){CN(Me)H}]+ and [Fe2(η-C5H5)2(CO)2{CN(Me)H}2]2+ salts (L = CO or CNMe)

The protonated species [Fe₂(η-C₅H₅)₂(CO)₂(η-CO){μ-CN(Me)H}]X, [Fe₂(η-C₅H₅)₂(CO)(CNMe)(μ-CO){μ-CN(Me)H}][X], and [Fe₂(η-C₅H₅)₂(CO)₂{η-CN(Me)H}₂][X]₂ react with one equivalent of AgY. The Ag⁺ and one H⁺ act together as a two-electron oxidant. Silver metal is precipitated quantitatively and the substrates cleaved to give mono-nuclear products of the type (a) [Fe(η-C₅H₅)(CO)(L)X] and [Fe(η-C₅H₅(CO)(L)Y] or (b) Fe(η-C₅H₅(CO)(L)(CNMe)][X] (L = CO, CNMe). If X⁻ and Y⁻ are both coordinating anions such as NO₃⁻, I⁻, or Br⁻ or the solvent is MeCN products of type (a) are usually obtained with X = Y = MeCN⁺ if acetonitrile is used as the solvent. However, if either X⁻ or Y⁻ is a non-coordinating anion such as BF₄⁻ or PF₆⁻ and methanol is the solvent, the products are usually those of type (b). When X⁻ = [p-MeC₆H₄SO₃]⁻, both types of products are obtained in significant amounts. If two equivalents of Ph₃P are added to the methanol solution of [Fe₂(η-C₅H₅)₂(CO)₂{-CN(Me)H}₂[BF₆]₂, no reaction takes place until the third equivalent of AgNO₃ has been added. The products have been isolated and characterized by analysis and infrared spectroscopy. The previously unreported [Fe₂(η-C₅H₅)₂(CO)(CNMe)(η-CO){η-CN(Me)H}] X salts are described for X⁻ = BF₄⁻, PF₆⁻, Br⁻ · 2H₂O, I⁻ · H₂O, NO₃⁻ · 0.5H₂O, and p-MeC₆H⁴SO₃⁻.     

Aluminum(III) Cations [(NHC) ⋅ AlMes2]+: Synthesis,Characterization, and Application in FLP-Chemistry

The three-coordinate aluminum cations ligated by N-heterocyclic carbenes (NHCs) [(NHC) ⋅ AlMes₂]⁺[B(C₆F₅)₄]⁻ (NHC=IMe^Me 4 , IiPr^Me 5 , IiPr 6 , Mes=2,4,6-trimethylphenyl) were prepared via hydride abstraction of the alanes (NHC) ⋅ AlHMes₂ (NHC=IMe^Me 1 , IiPr^Me 2 , IiPr 3 ) using [Ph₃C]⁺[B(C₆F₅)₄]⁻ in toluene as hydride acceptor. If this reaction was performed in diethyl ether, the corresponding four-coordinate aluminum etherate cations [(NHC) ⋅ AlMes₂(OEt₂)]⁺ [B(C₆F₅)₄]⁻ 7 – 9 (NHC=IMe^Me 7 , IiPr^Me 8 , IiPr 9 ) were isolated. According to a theoretical and experimental assessment of the Lewis-acidity of the [(IMe^Me) ⋅ AlMes₂]⁺ cation is the acidity larger than that of B(C₆F₅)₃ and of similar magnitude as reported for Al(C₆F₅)₃. The reaction of [(IMe^Me) ⋅ AlMes₂]⁺[B(C₆F₅)₄]⁻ 4 with the sterically less demanding, basic phosphine PMe₃ afforded a mixed NHC/phosphine stabilized cation [(IMe^Me) ⋅ AlMes₂(PMe₃)]⁺[B(C₆F₅)₄]⁻ 10 . Equimolar mixtures of 4 and the sterically more demanding PCy₃ gave a frustrated Lewis-pair (FLP), i.e., [(IMe^Me) ⋅ AlMes₂]⁺[B(C₆F₅)₄]⁻/PCy₃ FLP-11 , which reacts with small molecules such as CO₂, ethene, and 2-butyne.     

Radical Anions,Radical-Anion Salts,and Anionic Complexes of 2,1,3-Benzochalcogenadiazoles

By means of cyclic voltammetry (CV) and DFT calculations, it was found that the electron-acceptor ability of 2,1,3-benzochalcogenadiazoles 1 – 3 (chalcogen: S, Se, and Te, respectively) increases with increasing atomic number of the chalcogen. This trend is nontrivial, since it contradicts the electronegativity and atomic electron affinity of the chalcogens. In contrast to radical anions (RAs) [ 1 ]^.− and [ 2 ]^.−, RA [ 3 ]^.− was not detected by EPR spectroscopy under CV conditions. Chemical reduction of 1 – 3 was performed and new thermally stable RA salts [K(THF)]⁺[ 2 ]^.− ( 8 ) and [K(18-crown-6)]⁺[ 2 ]^.− ( 9 ) were isolated in addition to known salt [K(THF)]⁺[ 1 ]^.− ( 7 ). On contact with air, RAs [ 1 ]^.− and [ 2 ]^.− underwent fast decomposition in solution with the formation of anions [ECN]⁻, which were isolated in the form of salts [K(18-crown-6)]⁺[ECN]⁻ ( 10 , E=S; 11 , E=Se). In the case of 3 , RA [ 3 ]^.− was detected by EPR spectroscopy as the first representative of tellurium–nitrogen π-heterocyclic RAs but not isolated. Instead, salt [K(18-crown-6)]⁺₂[ 3 -Te₂]²⁻ ( 12 ) featuring a new anionic complex with coordinate Te−Te bond was obtained. On contact with air, salt 12 transformed into salt [K(18-crown-6)]⁺₂[ 3 -Te₄- 3 ]²⁻ ( 13 ) containing an anionic complex with two coordinate Te−Te bonds. The structures of 8 – 13 were confirmed by XRD, and the nature of the Te−Te coordinate bond in [ 3 -Te₂]²⁻ and [ 3 -Te₄- 3 ]²⁻ was studied by DFT calculations and QTAIM analysis.     

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)5}2]+ (M=Cu,Ag, Au)

Syntheses of the copper and gold complexes [Cu{Fe(CO)₅}₂][SbF₆] and [Au{Fe(CO)₅}₂][HOB{3,5-(CF₃)₂C₆H₃}₃] containing the homoleptic carbonyl cations [M{Fe(CO)₅}₂]⁺ (M=Cu, Au) are reported. Structural data of the rare, trimetallic Cu₂Fe, Ag₂Fe and Au₂Fe complexes [Cu{Fe(CO)₅}₂][SbF₆], [Ag{Fe(CO)₅}₂][SbF₆] and [Au{Fe(CO)₅}₂][HOB{3,5-(CF₃)₂C₆H₃}₃] are also given. The silver and gold cations [M{Fe(CO)₅}₂]⁺ (M=Ag, Au) possess a nearly linear Fe-M-Fe’ moiety but the Fe-Cu-Fe’ in [Cu{Fe(CO)₅}₂][SbF₆] exhibits a significant bending angle of 147° due to the strong interaction with the [SbF₆]⁻ anion. The Fe(CO)₅ ligands adopt a distorted square-pyramidal geometry in the cations [M{Fe(CO)₅}₂]⁺, with the basal CO groups inclined towards M. The geometry optimization with DFT methods of the cations [M{Fe(CO)₅}₂]⁺ (M=Cu, Ag, Au) gives equilibrium structures with linear Fe-M-Fe’ fragments and D₂ symmetry for the copper and silver cations and D_4d symmetry for the gold cation. There is nearly free rotation of the Fe(CO)₅ ligands around the Fe-M-Fe’ axis. The calculated bond dissociation energies for the loss of both Fe(CO)₅ ligands from the cations [M{Fe(CO)₅}₂]⁺ show the order M=Au (D_e=137.2 kcal mol⁻¹)>Cu (D_e=109.0 kcal mol⁻¹)>Ag (D_e=92.4 kcal mol⁻¹). The QTAIM analysis shows bond paths and bond critical points for the M−Fe linkage but not between M and the CO ligands. The EDA-NOCV calculations suggest that the [Fe(CO)₅]→M⁺←[Fe(CO)₅] donation is significantly stronger than the [Fe(CO)₅]←M⁺→[Fe(CO)₅] backdonation. Inspection of the pairwise orbital interactions identifies four contributions for the charge donation of the Fe(CO)₅ ligands into the vacant (n)s and (n)p AOs of M⁺ and five components for the backdonation from the occupied (n-1)d AOs of M⁺ into vacant ligand orbitals.     

Darstellung von Dithiatetrazocinen und Folgereaktionen

Preparation of Dithiatetrazocine and Secondary Reactions Li[PhCN₂(SiMe₃)₂] ( 1 ) or PhCN₂(SiMe₃)₃ ( 3 ) react with SCl₂ to give in good yields the dithiatetrazocine PhC(NSN)₂CPh ( 2 ). By analogy, p-MeC₆H₄C(NSN)₂CC₆H₄Me-p ( 7 ), p-NO₂C₆H₄C(NSN)₂-CC₆H₄NO₂-p ( 8 ), and p-CF₃C₆H₄C(NSN)₂CC₆H₄CF₃-p ( 9 ) are obtained from the reaction of p-MeC₆H₄CN₂(SiMe₃)₃ ( 4 ), Li[p-NO₂-C₆H₄CN₂(SiMe₃)₂] ( 5 ), und Li[p-CF₃C₆H₄CN₂(SiMe₃)₂] ( 6 ) with SCl₂. Reaction of 2 /LiCl with AgAsF₆ in liquid SO₂ leads to [PhCN₂S₂]⁺[AsF₆]⁻ ( 10 ) and 3[PhCN₂S₂]⁺2[AsF₆]⁻Cl⁻ ( 11 ). The structures of 10 and 11 are confirmed by X-ray analyses.     

Coordination Adducts of Niobium(V) and Tantalum(V) Azide M(N3)5 (M=Nb,Ta) with Nitrogen Donor Ligands and their Self‐Ionization

Several new donor–acceptor adducts of niobium and tantalum pentaazide with N‐donor ligands have been prepared from the pentafluorides by fluoride–azide exchange with Me₃SiN₃ in the presence of the corresponding donor ligand. With 2,2′‐bipyridine and 1,10‐phenanthroline, the self‐ionization products [MF₄(2,2′‐bipy)₂]⁺[M(N₃)₆]⁻, [M(N₃)₄(2,2′‐bipy)₂]⁺[M(N₃)₆]⁻ and [M(N₃)₄(1,10‐phen)₂]⁺[M(N₃)₆]⁻ were obtained. With the donor ligands 3,3′‐bipyridine and 4,4′‐bipyridine the neutral pentaazide adducts (M(N₃)₅)₂⋅L (M=Nb, Ta; L=3,3′‐bipy, 4,4′‐bipy) were formed.     

Novel 2-formylpyridine 4-allyl-S-methylisothiosemicarbazone and Zn(II), Cu(II), Ni(II) and Co(III) complexes: Synthesis,characterization, crystal structure,antioxidant, antimicrobial and antiproliferative activity

New zinc (II), copper (II), nickel (II) and cobalt (III) complexes, [Zn (HL)₂]I₂ (1) , [Cu (HL)Cl₂] (2) , [Cu (HL)Br₂] (3) , [Cu (HL)(H₂O)₂](ClO₄)₂ (4) , [Ni (HL)₂]I₂·H₂O (5) , [Co(L)₂]Cl (6) , [Co(L)₂]NO₃ (7) , [Co(L)₂]I·[Co(L)₂](I₃) (8) were obtained with 2-formylpyridine 4-allyl-S-methylisothiosemicarbazone ( HL ). The isothiosemicarbazone ligand was characterized by NMR (¹H and ¹³C), IR spectroscopy and X-ray diffraction. All the complexes were characterized by elemental analysis, IR, UV–Vis, ESI-MS spectroscopy, molar conductivity, magnetic susceptibility measurements. X-ray diffraction analysis on the monocrystal and powder elucidated the structure of the complexes 1 , 5 , 7 and 8 . The ligand and the complexes were tested for their antioxidant and antimicrobial activity against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae and Candida albicans. Also, the antiproliferative properties of these compounds on human leukemia HL-60, human cervical epithelial HeLa, human epithelial pancreatic adenocarcinoma BxPC-3, human muscle rhabdomyosarcoma spindle, large multinucleated RD cells and normal MDCK cells have been investigated. The nickel complex 5 and cobalt complexes 6 , 7 showed promising antiproliferative activity and low toxicity.     

CO Oxidation by Group 3 Metal Monoxide Cations Supported on [Fe(CO)4]2−

Infrared photodissociation spectroscopy of mass‐selected heteronuclear cluster anions in the form of OMFe(CO)₅⁻ (M=Sc, Y, La) indicates that all these anions involve an 18‐electron [Fe(CO)₄]²⁻ building block that is bonded with the M center through two bridged carbonyl ligands. The OLaFe(CO)₅⁻ anion is determined to be a CO‐tagged complex involving a [Fe(CO)₄]²⁻[LaO]⁺ anion core. In contrast, the OYFe(CO)₅⁻ anion is characterized to have a [Fe(CO)₄]²⁻[Y(η²‐CO₂)]⁺ structure involving a side‐on bonded CO₂ ligand. The CO‐tagged complex and the [Fe(CO)₄]²⁻[Sc(η²‐CO₂)]⁺ isomer co‐exist for the OScFe(CO)₅⁻ anion. These observations indicate that both the ScO⁺ and YO⁺ cations supported on [Fe(CO)₄]²⁻ are able to oxidize CO to CO₂. Theoretical analyses show that [Fe(CO)₄]²⁻ coordination significantly weakens the MO⁺ bond and decreases the energy gap of the interacting valence orbitals between MO⁺ and CO, leading to the CO oxidation reactions being both thermodynamically exothermic and kinetically facile.