Syntheses and structural analyses of chiral rhenium containing amines of the formula (η-C5H5)Re(NO)(PPh3)((CH2)nNRR′) (n = 0, 1)

The reaction of the racemic chiral methyl complex (η⁵-C₅H₅)Re(NO)(PPh₃)(CH₃) (1) with CF₃SO₃H and then NH₂CH₂C₆H₅ gives [(η⁵-C₅H₅)Re(NO)(PPh₃)(NH₂CH₂C₆H₅)]⁺ ([4a-H]⁺; 73%), and deprotonation with t-BuOK affords the amido complex (η⁵-C₅H₅)Re(NO)(PPh₃)(NHCH₂C₆H₅) (76%). Reactions of 1 with Ph₃C⁺ X⁻ and then primary or secondary amines give [(η⁵-C₅H₅)Re(NO)(PPh₃)(CH₂NHRR′)]⁺ X⁻ ([6-H]⁺ X⁻; R/R′/X = a, H/NH₂CH₂C₆H₅/BF₄; a′, H/NH₂CH₂C₆H₅/PF₆; b, H/NH₂CH₂(CH₂)₂CH₃/PF₆; c, H/(S)-NH₂CH(CH₃)C₆H₅/BF₄); d, CH₂CH₃/CH₂CH₃/PF₆; e, CH₂(CH₂)₂CH₃/CH₂(CH₂)₂CH₃/PF₆; f, CH₂C₆H₅/CH₂C₆H₅/PF₆; g, -CH₂(CH₂)₂CH₂-/PF₆; h, -CH₂(CH₂)₃CH₂-/PF₆; i, CH₃/CH₂CH₂OH/PF₆ (62-99%). Deprotonations with t-BuOK afford the amines (η⁵-C₅H₅)Re(NO)(PPh₃)(CH₂NRR′) (6a-i; 99-40%), which are more stable and isolated in analytically pure form when R ≠ H. Enantiopure 1 is used to prepare (R_ReS_C)-[6c-H]⁺, (R_ReS_C)-6c, (S)-[6g-H]⁺, and (S)-6g. The crystal structures of [4a-H]⁺, a previously prepared NH₂CH₂Si(CH₃)₃ analog, [6a′,d,f,h-H]⁺, (R_ReS_C)-6c, and 6f are determined and analyzed in detail, particularly with respect to cation/anion hydrogen bonding and conformation. In contrast to analogous rhenium containing phosphines, 6a-i show poor activities in reactions that are catalyzed by organic amines.     

Investigation of the MSO4 · xH2O (M = Zn, x = 7; M = Cd, x = 8/3)/methyl 2-pyridyl ketone oxime reaction system: A novel Cd(II) coordination polymer versus mononuclear and dinuclear Zn(II) complexes

The reactions of methyl 2-pyridyl ketone oxime, (py)C(Me)NOH, with MSO₄ · xH₂O (M = Zn, x = 7; M = Cd, x = 8/3), in the absence of an external base, have been investigated. The synthetic study has led to the two new complexes [Zn(SO₄){(py)C(Me)NOH}(H₂O)₃] · H₂O (1 · H₂O) and [Zn₂(SO₄)₂{(py)C(Me)NOH}₄] · (py)C(Me)NOH [2 · (py)C(Me)NOH], and the coordination polymer [Cd(SO₄){(py)C(Me)NOH}(H₂O)]_n · [Cd(SO₄){(py)C(Me)NOH}(H₂O)₂]_n (3). In the three complexes the organic ligand chelates through its nitrogen atoms. The sulfate anion in 1 · H₂O is monodentate; the complex molecule is the mer isomer considering the positions of the aqua ligands. The Zn^II centers in 2 · (py)C(Me)NOH are bridged by two syn, anti η¹:η¹:μ₂ ligands; each metal ion has the cis-cis-trans disposition of the coordinated sulfate oxygen, pyridyl nitrogen and oxime nitrogens, respectively. The molecular structure of 3 is unique consisting of two different linear and ladder - type chains. π-π stacking interactions and/or hydrogen bonds lead to the formation of interesting supramolecular architectures in the three complexes. The thermal decomposition of complex 3 has been studied. Characteristic vibrational (IR, Raman) bands are discussed in terms of the nature of bonding and the structures of the three complexes.     

Oxalate, squarate and croconate complexes with bis(2-pyrimidylcarbonyl)amidatecopper(II): synthesis, crystal structures and magnetic properties

The preparation and magnetic properties of three copper(II) compounds of formulae [Cu₂(bpcam)₂(H₂O)₂(C₂O₄)] (1), [Cu₂(bpcam)₂(H₂O)₄(C₄O₄)] · 10 H₂O (2) and Cu₂(bpcam)₂(C₅O₅)(H₂O)₃ (3) [bpcam = bis(2-pyrimidyl)amidate, and are reported. The structures of two of them (1 and 2) have been solved by single crystal X-ray diffraction and consists of centrosymmetric discrete copper(II) dinuclear units bridged by bis-bidentate oxalate (1) and bis-monodentate squarate (2), with the bpcam group acting as a terminal tridentate ligand. Each copper atom in 1 exhibits a distorted elongated octahedral coordination geometry. Three bpcam nitrogen atoms and one oxalate oxygen define the basal plane while the other oxalate oxygen and a water molecule take up the axial positions. Each copper atom in 2 is in an elongated octahedral surrounding with three bpcam nitrogen atoms and one squarate oxygen in the equatorial plane and two water molecules in the axial positions. The intramolecular copper-copper separations are 5.677(1) (1) and 7.819(53) Å (2). Magnetic susceptibility measurements for 1-3 in the temperature range 1.9-290 K show the occurrence of weak ferromagnetic interactions through oxalato (J = +0.75 cm⁻¹) and squarato (J = +1.26 cm⁻¹), the Hamiltonian being defined by . These values are analyzed and discussed in the light of the available magneto-structural data for analogous systems. The quasi-Curie law observed in 3 (θ = −1.15 K) contrasts with the significant antiferromagnetic interaction through bis-chelating croconate in other structurally characterized croconate-bridged copper(II) complexes and rules out the presence of bridging croconate in this compound.     

Synthesis and exploratory coordination chemistry of the new ditertiary carbinamine ligand 2,6-bis(α-aminoisopropyl)pyridine

The new pyridine-based N∩N∩N tridentate ligand 2,6-C₅H₃N(CMe₂NH₂)₂ (1) was synthesized by the treatment of 2,6-pyridinedicarbonitrile with an excess of the organocerium reagent in situ generated from CeCl₃ and methyllithium in THF. The reaction of 1 with [RuCl₂(PPh₃)₃] in THF at ambient conditions afforded (OC-6-23)-[RuCl{2,6-C₅H₃N(CMe₂NH₂)₂}(PPh₃)₂]Cl (2). The corresponding dimethyl sulfoxide complex [RuCl{2,6-C₅H₃N(CMe₂NH₂)₂}{S(O)Me₂}₂]Cl (3) was isolated as a mixture of the (OC-6-23) and (OC-6-32) stereoisomers 3a and 3b from the reaction between 1 and (OC-6-22)-[RuCl₂{S(O)Me₂}₃(OSMe₂)] in toluene at 80 °C. A prolonged interaction in toluene at reflux temperature gave isomerically pure 3a. The metal trichloride hydrates MCl₃ · xH₂O (M = Ru, Rh, Ir; x ≅ 2-4) produced mer-[RuCl₃{2,6-C₅H₃N(CMe₂NH₂)₂}] (M = Ru: 4; Rh: 5; Ir: 6), when combined with 1 in refluxing ethanol. The crystal structures of the following compounds were determined: ligand 1 and complexes 2-5 as addition compounds 2 · CH₂Cl₂, 3a · C₇H₈, 4 · EtOH and .     

Synthesis and reactivity with amines of new diiron alkynyl methoxy carbene complexes

The new diiron alkynyl methoxy carbene complexes [Fe₂{μ-CN(Me)(R)}(μ-CO)(CO){C(OMe)CCR′}(Cp)₂]⁺ (R = 2,6-Me₂C₆H₃ (Xyl), R′ = Tol, 3a; R = Xyl, R′ = Ph, 3b; R = Xyl, R′=Buⁿ, 3c; R = Xyl, R′=SiMe₃, 3d; R = Me, R′ = Tol, 3e; R = Me, R′ = Ph, 3f) are obtained in two steps by addition of R′CCLi (R′ = Tol, Ph, Buⁿ, SiMe₃) to the carbonyl aminocarbyne complexes [Fe₂{μ-CN(Me)(R)}(μ-CO)(CO)₂(Cp)₂]⁺ (R = Xyl, 1a; Me, 1b), followed by methylation of the resulting alkynyl acyl compounds [Fe₂{μ-CN(Me)(R)}(μ-CO)(CO){C(O)CCR′}(Cp)₂] (R = Xyl, R′ = Tol, 2a; R = Xyl, R′ = Ph, 2b; R = Xyl, R′ = Buⁿ, 2c; R = Xyl, R′ = SiMe₃, 2d; R = Me, R′ = Tol, 2e; R = Me, R′ = Ph, 2f). Complexes 3 react with secondary amines (i.e., Me₂NH, C₅H₁₀NH) to give the 4-amino-1-metalla-1,3-dienes [Fe₂{μ-CN(Me)(R)}(μ-CO)(CO){C(OMe)CHC(R′)(NMe₂)}(Cp)₂]⁺ (R = Xyl, R′ = Tol, 4a; R = Xyl, R′ = Ph, 4b; R = Me, R′ = Ph, 4c) and [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(Tol)(NC₅H₁₀)}(Cp)₂]⁺, 5. The addition occurs stereo-selectively affording only the E-configured products. Analogously, addition of primary amines R′NH₂ (R′ = Ph, Et, Prⁱ) affords the 4-(NH-amino)-1-metalla-1,3-diene complexes [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(R)(NHR′)}(Cp)₂]⁺ (R = Ph, 6a; Et, 6b; Prⁱ, 6c). In the case of 6a, only the E isomer is formed, whereas a mixture of the E and Z isomers is present in the case of 6b,c, with prevalence of the latter. Moreover, the two isomeric forms exist under dynamic equilibrium conditions, as shown by VT NMR studies. Complexes 6 are deprotonated by strong bases (e.g., NaH) resulting in the formation of the neutral vinyl imine complexes [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(NR)(Tol)}(Cp)₂] (R = Ph, 7a; Et, 7b; Prⁱ, 7c); the reaction can be reverted by addition of strong acids. X-ray crystal structures have been determined for 3a[CF₃SO₃] · Et₂O, 4c[CF₃SO₃], 6a[BF₄] · CH₂Cl₂, 6c[CF₃SO₃] · 0.5Et₂O and 7a · CH₂Cl₂.     

Syntheses and structures of Group 12 metal thioacetate anions, [M(SC{O}Me)nCl4−n] (n=3 and 4) and [Cd2Cl2(SC{O}Me)4]

We have utilized the possibility of altering the ratio of reactants to result in tetrahedral anions, [M(SC{O}Me)_nCl_4−n]²⁻ (n=3, 4) and [Cd₂Cl₂(SC{O}Me)₄]²⁻. Complexes of the formula [Ph₄P]₂[M(SC{O}Me)₄] (M=Zn(II) (1), Cd(II) (2) or Hg(II) (3)) were synthesized by the reaction of thioacetate ligand with the metal salts and Ph₄PCl in 4:1:2 molar ratio in suitable solvents. The geometry of Zn(II) in 1 is nearly tetrahedral and the distortion in tetrahedron increases in the order of 1<2<3 as observed from the SMS angles in the crystal structures. The tendency of monoanionic complexes [Ph₄P][M(SC{O}Me)₃] to react with 1 mole equivalent of Ph₄PCl resulted in complexes of the type [Ph₄P]₂[M(SC{O}Me)₃Cl] (M=Cd(II) (4) or Hg(II) (5)). In the structures of 4 and 5, three sulfur atoms and one chloride atom occupy the corners of the tetrahedron around the metal centers. However, in a 4:2:2 or 2:1:2 molar reaction of Me{O}CS⁻ with CdCl₂ and Ph₄PCl in aqueous medium resulted in a chloro bridged dimer, [Ph₄P]₂[Cd₂(μ-Cl)₂(SC{O}Me)₄] (6) as determined by X-ray crystallography.     

[Ir(acac)(η-C8H14)2]: A precursor in the synthesis of cyclometalated iridium(III) complexes

A new convenient synthesis and the crystallographic characterization of [Ir(acac)(coe)₂] (2, acac = acetylacetonato; coe = cis-cyclooctene) are described. The title compound crystallized from THF/ethanol in two modifications (monoclinic P2₁/c, 2a, and triclinic , 2b). Complex 2 represents an efficient starting material in the synthesis of mononuclear iridium(III) complexes containing cyclometalated 2-phenylpyridinato ligands using oxidative addition reactions of the corresponding ligands towards 2. Thus [Ir(acac)(ppy)₂] (3, ppy = 2-phenylpyridinato) and [Ir(ppy)₃] (4) (mer, 4a; fac, 4b) were prepared in excellent yields and short reaction times in a kind of one-pot procedure starting from [{Ir(μ-Cl)(coe)₂}₂] (1). Furthermore a convenient synthesis of [{Ir(μ-Cl)(ppy)₂}₂] (5) from 1 and Hppy is described.     

Reactivity of platina-β-diketones towards chelating nitrogen and sulfur donors: formation of acyl(hydrido)platinum(IV) and acyl(chloro)platinum(II) complexes

The platina-β-diketone [Pt₂{(COMe)₂H}₂(μ-Cl)₂] (1) was found to react with chelating N,N-ligands 2(R^′NCR)C₅H₄N (R/R^′=Ph/OH, H/Ph, Me/Ph) to form acyl(hydrido)platinum(IV) complexes [Pt(COMe)₂Cl(H){2-(R^′NCR)C₅H₄N}] (R/R^′=Ph/OH 2a; H/Ph 2b; Me/Ph (2c)). Reactions of complex 1 with chelating S,S- and N,S-donors (RS-CH₂-CH₂-SR, 2-(RSCH₂)C₅H₄N, R=Et, Ph, t-Bu) afforded acyl(chloro)platinum(II) complexes [Pt(COMe)Cl(RSCH₂CH₂SR)] (R=Et, 3a; Ph, 3b; t-Bu, 3c) and [Pt(COMe)Cl{2-(RSCH₂)C₅H₄N}] (R=Et, 4a; Ph, 4b; t-Bu, 4c), respectively. All complexes were fully characterized by microanalysis, IR and NMR (¹H, ¹³C) spectroscopy. Furthermore, molecular structures of complexes 3b and 4b were determined by single-crystal X-ray diffraction analyses revealing close to square-planar configuration. In complex 4b the acetyl ligand is trans to pyridine N atom (configuration index SP-4-2). The reactions are discussed in terms of consecutive oxidative addition and reductive elimination reactions.     

Copper complexes of tripodal κN-donor ligands: A structural, EPR spectroscopic and electrochemical study

A new tris(pyridylhydrazonyl)methane ligand, HC[N(Me)NC(H)Py]₃ (L2) (Py = pyridyl), has been synthesized. The latter is accessible from triethyl orthoformate and 2-(2-methylhydrazono)methylpyridine in 63% isolated yield. We have investigated its coordination chemistry towards copper ions and compared the results with those obtained for the recently developed multifunctional ligand, (S)P[N(Me)NC(H)Py]₃ (L1). The copper(II) complexes [Cu(L1)](OTf)₂ (3) and [Cu(L2)](OTf)₂ (4) (OTf = triflate, (O₃SCF₃)⁻) are mononuclear with the cations coordinated by three imino and three pyridine nitrogen atoms. Almost axial symmetric EPR spectra have been obtained in frozen solutions at X-band. The spectra show resolved hyperfine couplings to the copper nuclei on one of the three g values. X-ray structural analyses revealed in each case a cis bond distortion and a trigonal twist due to Jahn-Teller effects. The Cu^II/Cu^I reduction potentials of 3 and 4 were shown to be remarkably low ( = −0.11 V for 3;  = −0.34 V for 4), especially for 3 consisting of the phosphorus supported ligand L1. The corresponding copper(I) complexes [Cu(L1)](OTf) (5) and [Cu(L2)](OTf) (6) are accessible by reduction using decamethyl ferrocene. Both copper(I) complexes have been characterized in detail including X-ray structure analyses.     

Synthesis and cyclization reactions of platinum(II)-coordinated arsonium-substituted phenyl isocyanides, o-(IR3As-CH2)C6H4NC

The arsonium-substituted isocyanides, o-(I⁻⁺R₃AsCH₂)C₆H₄NC (AsR₃=AsPh₃, L₁; AsMePh₂, L₂; AsMe₂Ph, L₃), were prepared by reaction of o-(chloromethyl)phenyl isocyanide, o-(CH₂Cl)C₆H₄NC, with a slight molar stoichiometric amount of the arsine in the presence of a 3-fold excess of NaI in acetone at room temperature. The isocyanides L₁-L₃ coordinate to some Pt(II) complexes such as trans-[PtX{o-(I⁻⁺R₃AsCH₂)C₆H₄NC}(PPh₃)₂] [BF₄] (AsR₃=AsPh₃, 1; AsMePh₂, 2; AsMe₂Ph, 3; X=Cl, I) and [PtX{o-(I⁻⁺R₃AsCH₂)C₆H₄NC}(Ph₂PCHCHPPh₂)] [BF₄] (AsR₃=AsMePh₂, 4; X=Cl, I). Complexes 2-4 are converted in CH₂Cl₂ at room temperature in the presence of NEt₃ to the corresponding indolidin-2-ylidene derivatives trans-[PtX{(AsR₃)}(PPh₃)₂]BF₄] (AsR₃=AsPh₃, 5; AsMePh₂, 6; AsMe₂Ph, 7) and [PtX{(AsMePh₂)}(Ph₂PCHCHPPh₂)][BF₄] (8).     

Diiron and diruthenium aminocarbyne complexes containing pseudohalides: stereochemistry and reactivity

Acetonitrile is easily displaced from [Fe₂{μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp)₂][SO₃CF₃] (R = 2,6-Me₂C₆H₃ (Xyl) (1a); Me (1b)) upon stirring in THF at room temperature in the presence of [NBu₄][SCN]. The resulting complexes trans-[Fe₂{μ-CN(Me)(R)}(μ-CO)(CO)(NCS)(Cp)₂] (R = Xyl (trans-2a); Me (trans-2b)) are completely isomerised to cis-[Fe₂{μ-CN(Me)(R)}(μ-CO)(CO)(NCS)(Cp)₂] (R = Xyl (cis-2a); Me (cis-2b)) when heated at reflux temperature. Similarly, the complexes cis-[M₂{μ-CN(Me)(R)}(μ-CO)(CO)(NCO)(Cp)₂] (M = Fe, R = Me (4a); M = Ru, R = Xyl (4b); M = Ru, R = Me (4c)) and cis-[M₂{μ-CN(Me)(R)}(μ-CO)(CO)(N₃)(Cp)₂] (M = Fe, R = Xyl (5a); M = Fe, R = Me (5b); M = Ru, R = Xyl (5c)) can be obtained by heating at reflux temperature a THF solution of [M₂{μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp)₂][SO₃CF₃] (M = Fe, R = Xyl (1a); M = Fe, Me (1b); M = Ru, R = Xyl (1c); M = Ru, R = Me (1d)) in the presence of NaNCO and NaN₃, respectively. The reactions of 5 with MeO₂CCCCO₂Me, HCCCO₂Me and (NC)(H)CC(H)(CN) afford the triazolato complexes [M₂{μ-CN(Me)(R)}(μ-CO)(CO){N₃C₂(CO₂Me)₂}(Cp)₂] (M = Fe, R = Xyl (6a); M = Fe, R = Me (6b); M = Ru, R = Xyl (6c)), [M₂{μ-CN(Me)(R)}(μ- CO)(CO){N₃C₂(H)(CO₂Me)}(Cp)₂] (M = Fe, R = Me (7a); M = Ru, R = Xyl (7b)) and [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){N₃C₂(H)(CN)}(Cp)₂] (8), respectively. The asymmetrically substituted triazolato complexes 7-8 are obtained as mixtures of N(1) and N(2) bonded isomers, whereas 6 exists only in the N(2) form. Methylation of 6-8 results in the formation of the triazole complexes [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){N₃(Me)C₂(CO₂Me)₂}(Cp)₂][CF₃SO₃] (9), [M₂{μ-CN(Me)(R)}(μ-CO)(CO){N₃(Me)C₂(H)(CO₂Me)}(Cp)₂][CF₃SO₃] (M = Fe, R = Me (10a); M = Ru, R = Xyl (10b)) and [Fe₂{μ-CN(Me)(Xyl)}(μ-CO)(CO){N₃(Me)C₂(H)(CN)}(Cp)₂][CF₃SO₃], 11. The crystal structures of trans-2b, 4b · CH₂Cl₂, 5a, 6b · 0.5CH₂Cl₂ and 8 · CH₂Cl₂ have been determined.     

Chromium(III) complexes with 2-(2′-pyridyl)imidazole: Synthesis, crystal structure and magnetic properties

The preparation, crystal structure and variable temperature-magnetic investigation of three 2-(2′-pyridyl)imidazole-containing chromium(III) complexes of formula PPh₄[Cr(pyim)(C₂O₄)₂]·H₂O (1), AsPh₄[Cr(pyim)(C₂O₄)₂]·H₂O (2) and [Cr₂(pyim)₂(C₂O₄)₂(OH₂)₂]·2pyim · 6H₂O (3) [pyim = 2-(2′-pyridyl)imidazole, , and ] are reported herein. The isomorphous compounds are made up of discrete [Cr(pyim)(C₂O₄)₂]⁻ anions, cations [X = P (1) and As (2)] and uncoordinated water molecules. The chromium environment in 1 and 2 is distorted octahedral with Cr-N and Cr-O bond distances varying in the ranges 2.040(3)-2.101(3) and 1.941(3)-1.959(3) Å, respectively. The angle subtended by the chromium(III) ion by the two didentate oxalate ligands cover the range 82.49(12)-82.95(12)°, values which are somewhat greater than those concerning the chelating pyim molecule [77.94(13) (1) and 78.50(13)° (2)]. Complex 3 contains discrete centrosymmetric [Cr₂(pyim)₂(C₂O₄)₂(OH)₂] neutral units where the two chromium(III) ions are joined by a di-μ-hydroxo bridge, the oxalate and pyim groups acting as peripheral didentate ligands. Uncoordinated water and pyim molecules are also present in 3 and they contribute to the stabilization of its structure by extensive hydrogen bonding and π-π type interactions. The values of the intramolecular chromium-chromium separation and angle at the hydroxo bridge in 3 are 2.9908(12) Å and 99.60(16)°, respectively. Magnetic susceptibility measurements of 1-3 in the temperature range 1.9-300 K show the occurrence of weak inter- (1 and 2) and intramolecular (3) antiferromagnetic couplings. The magnetic properties of 3 have been interpreted in terms of a temperature-dependent exchange integral, small changes of the angle at the hydroxo bridge upon cooling being most likely responsible for this peculiar magnetic behavior.     

Squarato-metal(II) complexes. 1: Structural and magnetic characterization of squarato-bridged dinuclear nickel(II) and copper(II) complexes

A new series of dinuclear squarato-bridged nickel(II) and copper(II) complexes [Ni₂(2,3,2-tet)₂(μ_1,3-C₄O₄)(H₂O)₂](ClO₄)₂ (1), [Ni₂(aepn)₂(μ_1,3-C₄O₄)(H₂O)₂](ClO₄)₂ (2), [Cu₂(pmedien)₂(μ_1,3-C₄O₄)(H₂O)₂](ClO₄)₂.4H₂O (3) and [Cu₂(DPA)₂(μ_1,2-C₄O₄)(H₂O)₂](ClO₄)₂ (4) where is the dianion of 3,4-dihydroxycyclobut-3-en-1,2-dione (squaric acid), 2,3,2-tet = 1,4,8,11-tetraazaundecane, aepn = N-(2-aminoethyl)-1,3-propanediamine, pmedien = N,N,N′,N″,N″-pentamethyldiethylenetriamine and DPA = di(2-pyridylmethyl)amine were synthesized and structurally characterized by X-ray crystallography. The spectral and structural characterization as well as the magnetic behaviour of these complexes is reported. In this series, structures consist of the groups as counter ions and the bridging the two M(II) centers in a μ-1,3- (1-3) and in a μ-1,2-bis(monodentate) (4) bonding fashions. The coordination geometry around the Ni(II) ions in 1 and 2 is six-coordinate with distorted octahedral environment achieved by N atoms of the amines and by one or two oxygen atoms from coordinated water molecules, respectively. In the Cu(II) complexes 3 and 4, a distorted square pyramidal geometry is achieved by the three N-atoms of the aepn or DPA and by an oxygen atom from a coordinated water molecule. The electronic spectra of the complexes in aqueous solutions are in complete agreement with the assigned X-ray geometry around the M(II) centers. The complexes show weak antiferromagnetic coupling with ∣J∣ = 1.8-4.2 cm⁻¹ in the μ-1,3- bridged squarato compounds 1-3, and J = −16.1 cm⁻¹ in the corresponding μ-1,2- bridged squarato complex 4. The magnetic properties are discussed in relation to the structural data.     

Methimazole complexes of platinum(II): Synthesis, characterization and redox behavior

A variety of platinum(II) complexes of methimazole (2-mercapto-1-methylimidazole; HImS = neutral form and ImS = thiolate form), coordinated in both thione and thiolate forms, have been isolated by reacting methimazole with [PtCl(terpy)]Cl (terpy = 2,2′:6′,2″ terpyridine), [PtCl₂(bipy)] (bipy = bipyridine), [PtCl₂(o-phen)] (o-phen = o-phenanthroline), [PtCl₂(CH₃CN)₂] and [PtCl₂(COD)] (COD = 1,5-cyclooctadiene). These complexes were characterized by electronic absorption, IR and NMR (¹H, ¹³C, ¹⁹⁵Pt) spectroscopies. Molecular structure of [Pt(bipy)(HImS)₂]Cl₂·3H₂O (3a·3H₂O) has been established by single crystal X-ray crystallography. Platinum thiolate complex, [Pt(ImS)₂(HImS)₂] (5), could be obtained by treatment of [Pt(HImS)₄]Cl₂ with sodium methoxide in methanol. The solution of 5 in organic solvents yielded bi- and tri-nuclear platinum complexes. The effect of diimine ligands on oxidation of methimazole moiety in the complexes has been studied by electrochemical oxidation and pulse radiolytic oxidation employing specific one-electron oxidant, radical.     

Structural analysis and magnetic properties of the copper(II) dicyanamide complexes [Cu2(dmphen)2(dca)4], [Cu(dmphen)(dca)(NO3)]n and [Cu(4,4-dmbpy)(H2O)(dca)2] (dca=dicyanamide; dmphen=2,9-dimethyl-1,10-phenanthroline; 4,4-dmbpy=4,4-dimethyl-2,2-bipyridine)

The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu₂(dmphen)₂(dca)₄] (1), [Cu(dmphen)(dca)(NO₃)]_n (2) and [Cu(4,4^′-dmbpy)(H₂O)(dca)₂] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4^′-dmbpy=4,4^′-dimethyl-2,2^′-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen atoms of the dmphen molecule (1 and 2) and either one nitrile-nitrogen from a terminal dca ligand (1) or a nitrate-oxygen atom (2) build the equatorial plane whereas the second nitrogen atom of the heterocyclic dmphen fills the axial position (1 and 2). The copper-copper separations through double (1) and single (2) end-to-end dca bridges are 7.1337(7) (1) and 7.6617(7) (2). Compound 3 is a mononuclear copper(II) complex whose structure contains two neutral and crystallographically independent [Cu(4,4^′-dmbpy)(H₂O)(dca)₂] molecules which are packed in two different layer arrangements running parallel to the bc-plane and alternating along the a-axis. The copper atoms in both molecules have slightly distorted square pyramidal surroundings with the two nitrogen atoms of the 4,4^′-dmbpy ligand and two dca nitrile-nitrogen atoms in the basal plane and a water oxygen in the apical position. A semi co-ordinated dca nitrile-nitrogen from a neighbour unit [2.952(6) Å for Cu(2)-N] is in trans position to the apical water molecule in one of the two molecules, this feature representing part of the difference in supramolecular connections in the alternating layers referred to above. Magnetic susceptibility measurements for 1-3 in the temperature range 1.9-290 K reveal the occurrence of weak antiferromagnetic interactions through double [J=−3.3 cm⁻¹ (1), ] and single [J=−0.57 cm⁻¹ (2), ] dca bridges and across intermolecular contacts [θ=−0.07 K (3)].     

Cyclometalated rhodium(III) and iridium(III) complexes containing amino acids as N,O-chelates

The synthesis of bis-cyclometalated aminocarboxylato complexes [M(α-aminocarboxylato)(ptpy)₂] (M = Rh, 3, 4, 5; M = Ir, 6, 7, 8), ptpy = 2-(p-tolyl)pyridinato; aminocarboxylato = glycinato, l-alaninato, l-prolinato) from [{M(μ-Cl)(ptpy)₂}₂] (M = Rh, 1; M = Ir, 2) is described. The molecular structure of [Ir(l-alaninato)(ptpy)₂] (7) was confirmed by a single-crystal X-ray diffraction study. Compound 7 crystallized from methanol-iso-hexane in the space group P2₁. For 7 the two diastereoisomers Δ_Ir, S_C and Λ_Ir, S_C were found crystallizing twice per unit. Absorption and emission spectra were recorded. The rhodium compounds are weak yellow-green and the iridium species strong green emitters.     

Hybrid scorpionate/cyclopentadienyl titanium and zirconium complexes with alkoxide and imido ligands

The reactivity of hybrid scorpionate/cyclopentadienyl ligand-containing trichloride zirconium complexes [ZrCl₃(bpzcp)] (1) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] and [ZrCl₃(bpztcp)] (2) [bpztcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethylcyclopentadienyl] toward several lithium alkoxides has been carried out. Thus, alkoxide-containing complexes [ZrCl₂(OR)(bpzcp)] (R = Me, 3; Et, 4; ⁱPr, 5; (R)-2-Bu, 6), [ZrCl₂(OR)(bpztcp)] (R = Me, 7; Et, 8; ⁱPr, 9; (R)-2-Bu, 10) and [Zr(OR)₃(bpztcp)] (R = Et, 11; ⁱPr, 12) were prepared by deprotonation of the appropriate alcohol group with BuⁿLi followed by reaction with 1 or 2. In addition, the imido-complex [Ti(N^tBu)Cl(bpztcp)(py)] (13) were also prepared. The structures of these complexes have been proposed on basis of spectroscopic and DFT methods.     

Cd(II)-NCS/NCO complexes of 1-alkyl-2-(arylazo)imidazole: Single crystal X-ray structure of [Cd(HaaiMe)2(SCN)2]

The reaction of Cd(OAc)₂ · 4H₂O and 1-alkyl-2-(arylazo)imidazole [RaaiR′ where R = H (a), Me (b); R′ = Me (1/3/5), Et (2/4/6)] and NH₄NCS/NaNCO in methanol in 1:2:2 mole ratio has afforded [Cd(RaaiR′)₂(NCS)₂] (3, 4) and [Cd(RaaiR′)₂(NCO)₂] (5, 6) complexes. The complexes are characterized by different physicochemical methods and in one case, the structure was confirmed by single crystal X-ray diffraction study for title compounds.     

Palladium(II), platinum(II), ruthenium(II) and mercury(II) complexes of potentially tridentate Schiff base ligands of (E, N, O) type (E = S, Se, Te): Synthesis, crystal structures and applications in Heck and Suzuki coupling reactions

Schiff bases of 2-hydroxybenzophenone (HBP) (C₆H₅)(2-HOC₆H₄)CN(CH₂)_nEAr (L1/L2: E = S, Ar = Ph, n = 2/3; L3/L4: E = Se, Ar = Ph, n = 2/3; L5/L6: E = Te, Ar = 4-MeOC₆H₄, n = 2/3) and their complexes [PdCl(L-H)] (L = L1−L6; 1, 2, 3, 5, 7, 11), [PtCl(L3-H/L5-H)] (4/8), [PtCl₂(L4/L6)₂] (6/12), [(p-cymene)RuCl(L5/L6)]Cl (9/13) and [HgBr₂(L5/L6)₂] (10/14) have been synthesized and characterized by proton, carbon-13, selenium-77 and tellurium-125 NMR, IR and mass spectra. Single crystal structures of L1, 1, 3, 4, 5 and 7 were solved. The Pd-E bond distances (Å): 2.2563(6) (E = S), 2.3575(6)−2.392(2) (E = Se); 2.5117(5)−2.5198(5) (E = Te) are near the lower end of the bond length range known for them. The Pt-Se bond length, 2.3470(8) Å, is also closer to the short values reported so far. The Heck and Suzuki reaction were carried out using complexes 1, 3, 5 and 7 as catalysts under aerobic condition. The percentage yields for trans product in Heck reaction were found upto 85%.     

Reduction of diruthenium(II,III) carboxylate compounds with hydroquinone: a facile preparation of diruthenium(II) complexes

The synthesis of the diruthenium(II) compounds [Ru₂(μ-O₂CR)₄(MeOH)₂] [R = Me (1), Ph (2), CMePh₂ (3) C₆H₄-p-OMe (4), C₆H₄-p-CMe₃ (5)] by reaction of with hydroquinone, under a nitrogen atmosphere, in the presence of a base is described. This reaction constitutes an easy via to the preparation of diruthenium(II) compounds. The structure of the complexes [Ru₂(μ-O₂CMe)₄(MeOH)₂] (1) and [Ru₂(μ-O₂CPh)₄(thf)₂] (2b) is established by single crystal X-ray diffraction. These compounds show a diruthenium(II) unit bridged by four carboxylate ligands with the axial positions occupied by methanol and tetrahydrofuran molecules for 1 and 2b, respectively. Complex 1 shows, in the solid state, polymeric chains in which the molecules [Ru₂(μ-O₂CMe)₄(MeOH)₂] are linked by hydrogen bonds.