Synthesis and structure of a dmpe-substituted dinuclear complex bridged by a substituent-free gallium atom: Electronic effect of metal fragment on the iron–gallium bonding

A dinuclear complex bridged by a substituent-free gallium atom, Cp¹(dmpe)Fe–Ga–Fe(CO)₄ (1b: Cp¹ = η-C₅Me₅, dmpe = Me₂PCH₂CH₂PMe₂), was synthesized by the reaction of Cp¹Fe(dmpe)GaCl₂ with K₂[Fe(CO)₄]. Crystal structure analysis of complex 1b showed that the geometry around the gallium atom is essentially linear and the two Fe–Ga bonds are significantly shorter than those of usual single bonds, indicating the multiple bonding character of the Fe–Ga bonds. Comparison of the structure and IR data of 1b and those of Cp¹(dppe)Fe–Ga–Fe(CO)₄ (1a: dppe = Ph₂PCH₂CH₂PPh₂) revealed that the Fe–Ga bond is sensitive to the electronic character of the metal fragment. The Fe–Ga bond is shortened upon introducing a more π-basic metal fragment.     

Electronic structure of dinuclear iron nitrosyl complexes with different ligands at two iron centers

The electronic structures of three dinuclear iron complexes were determined with the DFT method. The complexes contain a {Fe(NO)₂}⁹ unit and thiolate, nitrosyl, carbonyl and amine ligands at the second iron atom. The two iron atoms are bridged by thiolate ligands. In the lowest energy states of these complexes, the iron atoms possess spin S = 1, 3/2 or 5/2, depending on the coordinated ligands and their mutual arrangement. Nitrosyl is coordinated as NO⁻ antiferromagnetically coupled to iron, and the two iron units are antiferromagnetically coupled to each other.     

Three new pseudohalide bridged dinuclear Zn(II) Schiff base complexes: Synthesis,crystal structures and fluorescence studies

Three new dinuclear Zn(II) complexes [Zn(L)(μ_1,1-N₃)Zn(L)(N₃)] · 1.5H₂O (1), [Zn(L)(μ_1,1-NCO)Zn(L)(NCO)] · 1.5H₂O (2) and [Zn(L)(μ_1,1-NCS)Zn(L)(NCS)(OH₂)] (3) have been synthesized from a potentially tetradentate N₂O₂-donor Schiff base ligand LH, [LH = (OCH₃)(OH)C₆H₃CHN(CH₂)₂N(CH₃)₂], which is the condensation product of o-vanillin and 2-dimethylaminoethylamine. All the three complexes 1, 2 and 3 have been characterized by elemental analysis, IR and ¹H NMR spectroscopy, TGA and fluorescence studies. Finally, their structures have been established by the single crystal X-ray diffraction method. Structural studies reveal that in complexes 1, 2 and 3 the two Zn(II) centers are held together by a μ₂-phenolato oxygen atom and also by an end-on pseudohalide nitrogen (azide for 1; cyanate for 2; thiocyanate for 3) atom. Among the two deprotonated Schiff base ligands present in each complex, one acts as a tetradentate ligand (N₂O₂ donor set) while the other acts as a tridentate ligand (N₂O donor set), having a non-coordinated methoxy group. All the synthesized complexes display intraligand ¹(π–π^∗) fluorescence and can potentially serve as photoactive materials.     

Analysis of spin states, spin barriers, and trans-effects involved in the coordination and stabilization of dinitrogen by biomimetic iron complexes

Coordination of dinitrogen to Sellmann-type iron (II) complexes in a sulfur-dominated coordination sphere, which emulates the environment of iron centers in the FeMo-cofactor of nitrogenase, is analyzed with respect to spin states, spin barriers, and the effect of trans-ligands. Such detailed investigations became only recently feasible when the reliability of density functional methods, which are the only quantum chemical methods capable of describing large transition metal complexes, could significantly be improved for the calculation of energies for states of different spin. It is found that the actual binding energy of dinitrogen is of sufficient magnitude for a reasonably strong fixation of N₂ by Sellmann-type coordination compounds. However, potential fixation is determined by additional factors which reduce the binding energy. One factor is the change in spin state of the N₂-free metal fragment, which lowers the total energy and quenches the thermodynamic stabilization effect of the binding energy. In addition, the metal fragment rearranges and gains even more stabilization energy for the un-coordinated state. Apart from these thermodynamical effects, the existence of spin barriers, which must be overcome upon binding of dinitrogen, leads to kinetical effects, which cannot be neglected.     

Characterization of imidazolate-bridged dinuclear and mononuclear hydroperoxo complexes

Dinucleating ligands having two metal-binding sites bridged by an imidazolate moiety, Hbdpi, HMe(2)bdpi, and HMe(4)bdpi (Hbdpi = 4,5-bis(di(2-pyridylmethyl)aminomethyl)imidazole, HMe(2)bdpi = 4,5-bis((6-methyl-2-pyridylmethyl)(2-pyridylmethyl)aminomethyl)imidazole, HMe(4)bdpi = 4,5-bis(di(6-methyl-2-pyridylmethyl)aminomethyl)imidazole), have been designed and synthesized as model ligands for copper-zinc superoxide dismutase (Cu,Zn-SOD). The corresponding mononucleating ligands, MeIm(Py)(2), MeIm(Me)(1), and MeIm(Me)(2) (MeIm(Py)(2) = (1-methyl-4-imidazolylmethyl)bis(2-pyridylmethyl)amine, MeIm(Me)(1) = (1-methyl-4-imidazolylmethyl)(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine, MeIm(Me)(2) = (1-methyl-4-imidazolyl-methyl)bis(6-methyl-2-pyridylmethyl)amine), have also been synthesized for comparison. The imidazolate-bridged Cu(II)-Cu(II) homodinuclear complexes represented as [Cu(2)(bdpi)(CH(3)CN)(2)](ClO(4))(3).CH(3)CN.3H(2)O (1), [Cu(2)(Me(2)bdpi)(CH(3)CN)(2)](ClO(4))(3) (2), [Cu(2)(Me(4)bdpi)(H(2)O)(2)](ClO(4))(3).4H(2)O (3), a Cu(II)-Zn(II) heterodinuclear complex of the type of [CuZn(bdpi)(CH(3)CN)(2)](ClO(4))(3).2CH(3)CN (4), Cu(II) mononuclear complexes of [Cu(MeIm(Py)(2))(CH(3)CN)](ClO(4))(2).CH(3)CN (5), [Cu(MeIm(Me)(1))(CH(3)CN)](ClO(4))(2)( )()(6), and [Cu(MeIm(Me)(2))(CH(3)CN)](ClO(4))(2)( )()(7) have been synthesized and the structures of complexes 5-7 determined by X-ray crystallography. The complexes 1-7 have a pentacoordinate structure at each metal ion with the imidazolate or 1-methylimidazole nitrogen, two pyridine nitrogens, the tertiary amine nitrogen, and a solvent (CH(3)CN or H(2)O) which can be readily replaced by a substrate. The reactions between complexes 1-7 and hydrogen peroxide (H(2)O(2)) in the presence of a base at -80 degrees C yield green solutions which exhibit intense bands at 360-380 nm, consistent with the generation of hydroperoxo Cu(II) species in all cases. The resonance Raman spectra of all hydroperoxo intermediates at -80 degrees C exhibit a strong resonance-enhanced Raman band at 834-851 cm(-1), which shifts to 788-803 cm(-1) (Deltanu = 46 cm(-1)) when (18)O-labeled H(2)O(2) was used, which are assigned to the O-O stretching frequency of a hydroperoxo ion. The resonance Raman spectra of hydroperoxo adducts of complexes 2 and 6 show two Raman bands at 848 (802) and 834 (788), 851 (805), and 835 (789) cm(-1) (in the case of H(2)(18)O(2), Deltanu = 46 cm(-1)), respectively. The ESR spectra of all hydroperoxo complexes are quite close to those of the parent Cu(II) complexes except 6. The spectrum of 6 exhibits a mixture signal of trigonal-bipyramid and square-pyramid which is consistent with the results of resonance Raman spectrum.     

Bonding trends of thiosemicarbazones in mononuclear and dinuclear copper(I) complexes: syntheses, structures, and theoretical aspects

Reactions of copper(I) halides with a series of thiosemicarbazone ligands (Htsc) in the presence of triphenylphosphine (Ph(3)P) in acetonitrile have yielded three types of complexes: (i) monomers, [CuX(eta1-S-Htsc)(Ph3P)2] [X, Htsc = I (1), Br (2), benzaldehyde thiosemicarbazone (Hbtsc); I (5), Br (6), Cl (7), pyridine-2-carbaldehyde thiosemicarbazone (Hpytsc)], (ii) halogen-bridged dimers, [Cu2(mu2-X)2(eta1-S-Htsc)2(Ph3P)2] [X, Htsc = Br (3), Hbtsc; I (8), furan-2-carbaldehyde thiosemicarbazone (Hftsc); I (11), thiophene-2-carbaldehyde thiosemicarbazone (Httsc)], and (iii) sulfur-bridged dimers, [Cu2X2(mu2-S-Htsc)2(Ph3P)2] [X, Htsc = Cl (4), Hbtsc; Br (9), Cl (10), pyrrole-2-carbaldehyde thiosemicarbazone (Hptsc); Br (12), Httsc]. All of these complexes have been characterized with the help of elemental analysis, IR, 1H, 13C, or 31P NMR spectroscopy, and X-ray crystallography (1-12). In all of the complexes, thiosemicarbazones are acting as neutral S-donor ligands in eta()S or mu2-S bonding modes. The Cu...Cu separations in the Cu(mu2-X)2Cu and Cu(mu2-S)2Cu cores lie in the ranges 2.981(1)-3.2247(6) and 2.813(1)-3.2329(8) Angstroms, respectively. The geometry around each Cu center in monomers and dimers may be treated as distorted tetrahedral. Ab initio density functional theory calculations on model monomeric and dimeric complexes of the simplest thiosemicarbazone [H2C=N-NH-C(S)-NH2, Htsc] have revealed that monomers and halogen-bridged dimers have similar stability and that sulfur-bridged dimers are stable only when halogen atoms are engaged in hydrogen bonding with the solvent of crystallization or H2O molecules.     

Electronic properties of mononuclear, dinuclear, and polynuclear cobaltacarboranes: electrochemical and spectroelectrochemical studies

Electronic interactions and metal-metal communication in a wide range of cobaltacarborane-hydrocarbon complexes containing one to six metal centers, and exhibiting a variety of modes of inter-cage connectivity and molecular architectures, have been investigated via cyclic voltammetry, controlled potential coulometry, and UV-visible spectroelectrochemistry. The properties of mixed-valent Co(III)/Co(IV) and Co(II)/Co(III) species that are generated on oxidation or reduction of dinuclear and polynuclear Co(III) complexes were examined and classified as Robin-Day Class I (localized), Class II (partially delocalized), or Class III (fully delocalized) systems. The extent of metal-metal communication between metallacarborane cage units is strongly influenced by the type of intercage connection (e.g., cage B-B or Cp-Cp); the vertexes involved (equatorial vs apical); the nature of the linking unit, if any; and the presence of substituents on the carborane cages. In multi-tripledecker complexes where three CpCo(C(2)B(3)H(4))CoCp units are linked through a central triethynyl benzene connector, the data suggest that Co-Co electronic communication is extensive (Class III) within individual sandwich units while intersandwich delocalization is weak or absent. An extended Hückel study of CpCoC(2)B(4)H(6) double-decker and CpCo(C(2)B(3)H(5))CoCp triple-decker sandwich model complexes shows significant differences in the orbital contributions involved in the HOMO and LUMO of the former vs the latter type. The calculations afford additional insight into the electronic structures and properties of these systems as elucidated by the experimental studies.     

Five dinuclear iron carbonyl complexes based on substituted tetramethylcyclopentadienyl ligands: synthesis and crystal structures

Thermal treatment of the substituted tetramethylcyclopentadienes [C₅Me₄HR] [R?=?n-propyl (1), i-propyl (2), cyclopentyl (3), cyclohexyl (4), and 4-NMe₂Ph (5)] with Fe(CO)₅ gave five new substituted tetramethylcyclopentadienyl dinuclear iron carbonyl complexes, [η⁵-C₅Me₄CH₂CH₂CH₃]₂Fe₂(CO)₄ (6), [η⁵-C₅Me₄CH(CH₃)₂]₂Fe₂(CO)₄ (7), [η⁵-C₅Me₄CH(CH₂)₄]₂Fe₂(CO)₄ (8), [η⁵-C₅Me₄CH(CH₂)₅]₂Fe₂(CO)₄ (9), and [(η⁵-C₅Me₄)(4-NMe₂Ph)]₂Fe₂(CO)₄ (10). The new complexes were characterized by elemental analysis, IR, and ¹H NMR spectra. The molecular structures of 6, 8, 9, and 10 were determined by X-ray single crystal diffraction.     

C-H Activation by dinuclear phosphine bridged complexes of rhodium,iridium, and ruthenium

The possibility of activation of the C-H bond by dinuclear phosphine bridged complexes of rhodium, iridium, and ruthenium is considered.This work was reported at the conference Modern Problems of Organometallic Chemistry (8–13 May, 1994, Moscow).Institut fer Technische Chemie und Petrolchemie der RWTH Aachen Worringerweg 1, 52074 Aachen, Deutschland.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 589–593, April, 1994.     

Structure, energetics, and bonding of first row transition metal pentazolato complexes: a DFT study

Quantum chemical calculations with gradient-corrected (B3LYP) density functional theory for the mono- and bispentazolato complexes of the first row transition metals (V, Cr, Mn, Fe, Co, and Ni), the all-nitrogen counterparts of metallocenes, were performed, and their stability was investigated. All possible bonding modes (e.g. eta1, eta2, eta3, and eta5) of the pentazolato ligand to the transition metals have been examined. The transition metal pentazolato complexes are predicted to be strongly bound molecules. The computed total bond dissociation enthalpies that yield free transition metal atoms in their ground states and the free pentazolato ligands were found in the range of 122.0-201.9 (3.7-102.3) kcal mol(-1) for the bispentazolato (monopentazolato) complexes, while those yielding M2+ and anionic pentazolato ligands were found in the range of 473.2-516.7 (273.6-353.5) kcal mol(-1). The electronic ground states of azametallocenes along with their spectroscopic properties (IR, NMR, and UV-vis) obtained in a consistent manner across the first transition metal series provide means for discussion of their electronic and bonding properties, the identification of the respective azametallocenes, and future laboratory studies. Finally, exploring synthetic routes to azametallocenes it was found that a [2 + 3] cycloaddition of dinitrogen to a coordinated azide ligand with nickel(II) does not seem to provide a promising synthetic route for transition metal pentazolato complexes while the oxidative addition of phenylpentazole and fluoropentazole to Ni(0) bisphosphane complexes merits attention for the experimentalists.     

Synthesis,characterization, and antitumor activity of mononuclear and dinuclear ruthenium complexes

Abstract

Dinuclear ruthenium complexes [Ru₂(bpy)₄BL](ClO₄)₂ (Ru-1), where bpy = 2,2′-bipyridine and BL = 2,2′-((1E,1′E)-((E)-diazene-1,2-diyl-bis(2,1-phenylene))-bis(azanylylidene))bis(methanylylidene))diphenol (a bidentate bridging ligand), and mononuclear ruthenium complexes [Ru(bpy)₂L](ClO₄) (Ru-2), where L = (E)-2-((phenylimino)methyl)phenol, were synthesized and characterized by elemental analysis and electrospray ionization mass spectrometry. Their photophysical and electrochemical properties were also studied. The cytotoxicity of the two complexes in vitro was evaluated using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. The results indicated that Ru-1 and Ru-2 exhibited significant dose-dependent cytotoxicity to human breast cancer (MCF-7), gastric cancer (SGC-7901), cervical cancer (Hela), and lung cancer (A549) tumor cell lines. Ru-1 showed excellent antitumor effects in a cellular study (IC₅₀ values of 3.61 μM for MCF-7 human breast cancer cells in vitro). However, Ru-2 exhibited the highest cytotoxicity to Hela cells; the IC₅₀ value is 3.71 μM. The results reveal that Ru-1 and Ru-2 have obvious selectivity and might be a potential anticancer agent that could improve the efficacy of common anticancer therapies.     

Electronic structure of mononuclear bis(1,2-diaryl-1,2-ethylenedithiolato)iron complexes containing a fifth cyanide or phosphite ligand: a combined experimental and computational study

A series of mononuclear square-based pyramidal complexes of iron containing two 1,2-diaryl-ethylene-1,2-dithiolate ligands in various oxidation levels has been synthesized. The reaction of the dinuclear species [Fe(III)2(1L*)2(1L)2]0, where (1L)2- is the closed shell di-(4-tert-butylphenyl)-1,2-ethylenedithiolate dianion and (1L*)1- is its one-electron-oxidized pi-radical monoanion, with [N(n-Bu)4]CN in toluene yields dark green crystals of mononuclear [N(n-Bu)4][Fe(II)(1L*)2(CN)] (1). The oxidation of 1 with ferrocenium hexafluorophosphate yields blue [Fe(III)(1L*)2(CN)] (1ox), and analogously, a reduction with [Cp2Co] yields [Cp2Co][N(n-Bu)4][Fe(II)(1L*)(1L)(CN)] (1red); oxidation of the neutral dimer with iodine gives [Fe(III)(1L*)2I] (2). The dimer reacts with the phosphite P(OCH3)3 to yield [Fe(II)(1L*)2{P(OCH3)3}] (3), and [Fe(III)2(3L*)2(3L)2] reacts with P(OC6H5)3 to give [Fe(II)(3L*)2{P(OC6H5)3}] (4), where (3L)2- represents 1,2-diphenyl-1,2-ethylenedithiolate(2-). Both 3 and 4 were electrochemically one-electron oxidized to the monocations 3ox and 4ox and reduced to the monoanions 3red and 4red. The structures of 1 and 4 have been determined by X-ray crystallography. All compounds have been studied by magnetic susceptibility measurements, X-band EPR, UV-vis, IR, and M?ssbauer spectroscopies. The following five-coordinate chromophores have been identified: (a) [Fe(III)(L*)2X]n, X = CN-, I- (n = 0) (1ox, 2); X = P(OR)3 (n = 1+) )3ox, 4ox) with St = 1/2, SFe = 3/2; (b) [Fe(II)(L*)2X]n, X = CN-, (n = 1-) (1); X = P(OR)3 (n = 0) (3, 4) with St = SFe = 0; (c) [Fe(II)(L*)(L)X]n <--> [Fe(II)(L)(L*)X]n, X = CN- (n = 2-) (1red); X = P(OR)3 (n = 1-) (3red, 4red) with St = 1/2, SFe = 0 (or 1). Complex 1ox displays spin crossover behavior: St = 1/2 <--> St = 3/2 with intrinsic spin-state change SFe = 3/2 <--> SFe = 5/2. The electronic structures of 1 and 1(ox) have been established by density functional theoretical calculations: [Fe(II)(1L*)2(CN)]1- (SFe = 0, St = 0) and [Fe(III)(1L*)2(CN)]0 (SFe = 3/2, St = 1/2).     

The molecular structure, bonding, and energetics of oxovanadium phthalocyanine: an experimental and computational study

A mass spectrometric study of saturated vapor over oxovanadium phthalocyanine showed the thermal stability and monomeric vapor composition of this compound. The molecular structure of oxovanadium phthalocyanine (VOPc) was determined using a combination of gas-phase electron diffraction (GED), mass spectrometry, and quantum chemical calculations. According to GED, the VOPc molecule has C_4v symmetry. Experimental structural parameters are in good agreement with the parameters obtained by UB3LYP/cc-pVTZ calculations. The vanadium atom has a five-coordinated square-pyramidal geometry, being shifted above the plane of the four isoindole nitrogen atoms by 0.576(14) Å. The parameters of the square pyramid VN₄ are r _h1(V–N) = 2.048(7) Å, r _h1(N···N) = 2.780(12) Å. The vanadium–oxygen bond length is r _h1(V–O) = 1.584(11) Å. NBO analysis shows polar character of coordination bonds with significant covalent contribution and pronounced direct donation. X-ray crystallography and GED give different coordination bond lengths according to the different physical meaning of the parameters obtained by these methods. The enthalpy of sublimation [?H _s ^o (593–678 K)] is 53.3 ± 0.8 kcal/mol.     

Dinuclear ruthenium and iron complexes containing palladium and platinum with tri-tert-butylphosphine ligands: synthesis, structures, and bonding

The reaction of Pd(PBu(t)(3))(2) with Ru(CO)(5) yielded the dipalladium-diruthenium cluster complex Ru(2)(CO)(9)[Pd(PBu(t)(3))](2), 10. The reaction of Pt(PBu(t)(3))(2) with Ru(CO)(5) at room temperature afforded the diplatinum-diruthenium cluster complex Ru(2)(CO)(9)[Pt(PBu(t)(3))](2), 12, and the monoplatinum-diruthenium cluster PtRu(2)(CO)(9)(PBu(t)(3)), 11. All three complexes contain a diruthenium group with bridging Pd(PBu(t)(3)) or Pt(PBu(t)(3)) groups. Compound 11 can be converted to 12 by reaction with an additional quantity of Pt(PBu(t)(3))(2). The reaction of 12 with hydrogen at 68 degrees C yielded the dihydrido complex Pt(2)Ru(2)(CO)(8)(PBu(t)(3))(2)(micro-H)(2), 13. This complex contains a Ru(2)Pt(2) cluster with hydride ligands bridging two of the Ru-Pt bonds. The reaction of Fe(2)(CO)(9) with Pt(PBu(t)(3))(2) yielded the platinum-diiron cluster complex PtFe(2)(CO)(9)(PBu(t)(3)), 14, which is analogous to 11. All new complexes were characterized crystallographically. Molecular orbital calculations of 10 reveal an unusual delocalized metal-metal bonding system involving the Pd(PBu(t)(3)) groups and the Ru(2)(CO)(9) group.     

Proton control of oxidation and spin state in a series of iron tripodal imidazole complexes

Reaction of iron salts with three tripodal imidazole ligands, H(3)(1), H(3)(2), H(3)(3), formed from the condensation of tris(2-aminoethyl)amine (tren) with 3 equiv of an imidazole carboxaldehyde yielded eight new cationic iron(III) and iron(II), [FeH(3)L](3+or2+), and neutral iron(III), FeL, complexes. All complexes were characterized by EA(CHN), IR, UV, M?ssbauer, mass spectral techniques and cyclic voltammetry. Structures of three of the complexes, Fe(2).3H(2)O (C(18)H(27)FeN(10)O(3), a = b = c = 20.2707(5), cubic, I3d, Z = 16), Fe(3).4.5H(2)O (C(18)H(30)FeN(10)O(4.5), a = 20.9986(10), b = 11.7098(5), c = 19.9405(9), beta = 109.141(1), monoclinic, P2(1)/c), Z = 8), and [FeH(3)(3)](ClO(4))(2).H(2)O (C(18)H(26)Cl(2)FeN(10)O(9), a = 9.4848(4), b = 23.2354(9), c = 12.2048(5), beta = 111.147(1) degrees, monoclinic, P2(1)/n, Z = 4) were determined at 100 K. The structures are similar to one another and feature an octahedral iron with facial coordination of imidazoles and imine nitrogen atoms. The iron(III) complexes of the deprotonated ligands, Fe(1), Fe(2), and Fe(3), are low-spin while the protonated iron(III) cationic complexes, [FeH(3)(1)](ClO(4))(3) and [FeH(3)(2)](ClO(4))(3), are high-spin and spin-crossover, respectively. The iron(II) cationic complexes, [FeH(3)(1)]S(4)O(6), [FeH(3)(2)](ClO(4))(2), [FeH(3)(3)](ClO(4))(2), and [FeH(3)(3)][B(C(6)H(5))(4)](2) exhibit spin-crossover behavior. Cyclic voltammetric measurements on the series of complexes show that complete deprotonation of the ligands produces a negative shift in the Fe(III)/Fe(II) reduction potential of 981 mV on average. Deprotonation in air of either cationic iron(II) or iron(III) complexes, [FeH(3)L](3+or2+), yields the neutral iron(III) complex, FeL. The process is reversible for Fe(3), where protonation of Fe(3) yields [FeH(3)(3)](2+).     

Synthesis and characterization of dinuclear pyrazolato bridged platinum(IV) complexes

Reactions of [PtMe₃(OCMe₂)₃](BF₄) and [(PtMe₃I)₄] with pyrazole (pzH) afforded mononuclear pyrazole platinum(IV) complexes [PtMe₃(pzH)₃](BF₄) (1) and [PtMe₃I(pzH)₂] (2), respectively. The formation of dinuclear pyrazolato bridged platinum(IV) complexes (PPN)[(PtMe₃)₂(μ-pz)₃] (3), (PPN)[(PtMe₃)₂(μ-I)(μ-pz)₂] · 1/2Et₂O (4) and [K(18C6)][(PtMe₃)₂(μ-I)(μ-pz)₂] (5) was achieved by the reaction of each 1 and 2 with [PtMe₃(OCMe₂)₃](BF₄) in the presence of KOAc followed by reaction with (PPN)Cl (PPN⁺ = bis(triphenylphosphine)iminium cation) and 18C6, respectively. The reaction of complex 4 with AgO₂CCF₃ followed by addition of RSR′ (R/R′ = Me/Me, Me/Ph) resulted in the formation of complexes [(PtMe₃)₂(μ-pz)₂(μ-RSR′)] (R/R′ = Me/Me, 6; Me/Ph, 7). All complexes were characterized unambiguously by microanalysis and NMR (¹H, ¹³C) spectroscopic investigations. Additionally, crystal structures of complexes 3 and 4 as well as DFT calculation are presented. Furthermore, in vitro studies on the anti-proliferative activity of complexes 2 and 5 were carried out.     

Active-site models for iron hydrogenases: reduction chemistry of dinuclear iron complexes

Reduction of Fe2(mu-S2C3H6)(CO)6 (1) in tetrahydrofuran with 1 equiv of decamethylcobaltocene (Cp*2Co) affords a tetranuclear dianion 2. The IR spectra of samples of 2 in solution and in the solid state exhibit a band at 1736 cm(-1), suggestive of the presence of a bridging carbonyl (CO) ligand. X-ray crystallography confirms that the structure of 2 consists of two Fe2 units bridged by a propanedithiolate moiety formulated as [Fe2(mu-S2C3H6)(CO)5(SCH2CH2CH2-mu-S)Fe2(mu-CO)(CO)6](2-). One of the Fe2 units has a bridging CO ligand and six terminal CO ligands. The second subunit exhibits a bridging propanedithiolate moiety. One CO ligand has been replaced by a terminal thiolate ligand, replicating the basic architecture of Fe-only hydrogenases. The reduction reaction can be reversed by treatment of 2 with 2 equiv of [Cp2Fe][PF6], reforming complex 1 in near-quantitative yield. Complex 2 can also be oxidized by acids such as p-toluenesulfonic acid, regenerating complex 1 and forming H2.     

Synthesis and structures of bridged biscyclopentadienyl diiron complexes

Three diiron carbonyl complexes, namely [(η ⁵-C₅H₄)(η ³-C(CH₂)₂)]Fe₂(CO)₅ (1), [(C₂H₅)₂C(η ⁵-C₅H₄)₂]Fe₂(μ-CO)₂(CO)₂ (2), and [(CH₂)₄C(η ⁵-C₅H₄)(η ⁵-C₅H₃)(C₅H₉)]Fe₂(μ-CO)₂(CO)₂ (3), have been synthesized by the reactions of C₅H₄C(Me)₂, C₅H₄C(Et)₂, and C₅H₄C(CH₂)₄, respectively, with Fe(CO)₅ in refluxing xylene. The complexes have been characterized by elemental analysis, IR, and ¹H NMR spectra. The molecular structures of the complexes have been determined by single-crystal X-ray diffraction. The structures of the complexes indicate that fulvenes can be bound to transition metal centers by diverse modes.     

Electronic structure, bonding, spectroscopy and energetics of Fe-dependent nitrile hydratase active-site models

Fe-type nitrile hydratase (NHase) is a non-heme Fe(III)-dependent enzyme that catalyzes the hydration of nitriles to the corresponding amides. Despite experimental studies of the enzyme and model Fe(III)-containing complexes, many questions concerning the electronic structure and spectroscopic transitions of the metal center remain unanswered. In addition, the catalytic mechanism of nitrile hydration has not yet been determined. We now report density functional theory (B3LYP/6-31G) calculations on three models of the Fe(III) center in the active site of NHase corresponding to hypothetical intermediates in the enzyme-catalyzed hydration of acetonitrile. Together with natural bond orbital (NBO) analysis of the chemical bonding in these active-site models and INDO/S CIS calculations of their electronic spectra, this theoretical investigation gives new insight into the molecular origin of the unusual low-spin preference and spectroscopic properties of the Fe(III) center. In addition, the low-energy electronic transition observed for the active form of NHase is assigned to a dd transition that is coupled with charge-transfer transitions involving the metal and its sulfur ligands. Calculations of isodesmic ligand-exchange reaction energies provide support for coordination of the Fe(III) center in free NHase by a water molecule rather than a hydroxide ion and suggest that the activation of the nitrile substrate by binding to the metal in the sixth coordination site during catalytic turnover cannot yet be definitively ruled out.