Ruthenium(II) Complexes with Three Different Diimine Ligands

The synthesis of tri-heteroleptic complex of Ru(II) with diimine ligands is describe. Ten compounds [Ru(R₂bpy) (biq) (L)][PF₆]₂ (R = H, CH₃); L = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (Me₂bpy), 2,2′-bipyrimidine (bpm), 2,2′-biisoquinoline (biiq), 1,10-phenanthroline (phen), dipyrido[3,2-c:2′,3′-e]pyridazine (taphen), 2,2′-biquinoline (biq), 6,7-dihydrodipyrido[2,3-b:3,2-j][1,10]-phenanthroline (dinapy), 2-(2[pyridyl)quinoline (pq), 1-(2-pyrimidyl)pyrazole] (pzpm), 2,2′-biimidazole (H₂biim) are characterized by elemental analysis, electronic and ¹H-NMR spectroscopy. The relative photosustitution rates of biq in MeCN are given at three temperatures.     

A theoretical and experimental study on the Lewis acid-base adducts (P(4)E(3)).(BX(3)) (E = S, Se; X = Br, I) and (P(4)Se(3)).(NbCl(5))

The Lewis acid-base adducts (P(4)E(3)).(BX(3)) (E = S, Se; X = Br, I) and (P(4)Se(3)).(NbCl(5)) have been prepared and characterized by Raman, IR, and solid-state (31)P MAS NMR spectroscopy. Hybrid density functional calculations (B3LYP) have been carried out for both the apical and the basal (P(4)E(3)).(BX(3)) (E = S, Se; X = Br, I) adducts. The thermodynamics of all considered species has been discussed. In accordance with solid-state (31)P MAS NMR and vibrational data, the X-ray powder diffraction structures of (P(4)S(3)).(BBr(3)) [monoclinic, space group P2(1)/m (No. 11), a = 8.8854(1) A, b = 10.6164(2) A, c = 6.3682(1) A, beta = 108.912(1) degrees, V = 568.29(2) A(3), Z = 2] and (P(4)S(3)).(BI(3)) [orthorhombic, space group Pnma (No. 62), a = 12.5039(5) A, b = 11.3388(5) A, c = 8.9298(4) A, V = 1266.09(9) A(3), Z = 4] indicate the formation of an apical P(4)S(3) complex in the reaction of P(4)S(3) with BX(3) (X = Br, I). Basal adducts are formed when P(4)Se(3) is used as the donor species. Vibrational assignment for the normal modes of these adducts has been made on the basis of comparison between theoretically obtained and experimentally observed vibrational data.     

E4 Butterfly Complexes (E=P,As) as Chelating Ligands

The coordination properties of new types of bidentate phosphane and arsane ligands with a narrow bite angle are reported. The reactions of [{Cp′′′Fe(CO)₂}₂(μ,η^1:1‐P₄)] ( 1 a ) with the copper salt [Cu(CH₃CN)₄][BF₄] leads, depending on the stoichiometry, to the formation of the spiro compound [{{Cp′′′Fe(CO)₂}₂(μ₃,η^1:1:1:1‐P₄)}₂Cu]⁺[BF₄]^? ( 2 ) or the monoadduct [{Cp′′′Fe(CO)₂}₂(μ₃,η^1:1:2‐P₄){Cu(MeCN)}]⁺[BF₄]^? ( 3 ). Similarly, the arsane ligand [{Cp′′′Fe(CO)₂}₂(μ,η^1:1‐As₄)] ( 1 b ) reacts with [Cu(CH₃CN)₄][BF₄] to give [{{Cp′′′Fe(CO)₂}₂(μ₃,η^1:1:1:1‐As₄)}₂Cu]⁺[BF₄]^? ( 5 ). Protonation of 1 a occurs at the “wing tip” phosphorus atoms, which is in line with the results of DFT calculations. The compounds are characterized by spectroscopic methods (heteronuclear NMR spectroscopy and IR spectrometry) and by single‐crystal X‐ray diffraction studies.     

Octahedral Tin(IV) Complexes of the Chalcogen‐Centered Ligands [EC(PPh2S)2]2– (E = S,Se)

The metathetical reactions between SnBr₄ and Li₂[E'C(PPh₂E)₂] in toluene produce the homoleptic tin(IV) complexes Sn[E′C(PPh₂E)₂]₂ [E = E′ = S ( 1b ); E = S, E′ = Se ( 1c )], which were isolated as red crystals and structurally characterized by X‐ray crystallography. The metrical parameters of these octahedral complexes are compared with those of the all‐selenium analog Sn[E′C(PPh₂E)₂]₂ (E = E′ = Se, 1a ), which was prepared previously by a different route.     

E2(CN)2 (E = S, Se) and related compounds

A synthetic, spectroscopic, and theoretical study of Ex(CN)2 (E = S, Se; x = 1-3) is described. The X-ray structures of Se2(CN)2 and Se3(CN)2 have been determined. Se2(CN)2 crystallizes in a chiral space group with the CN groups approximately gauche.     

Synthesis and Structures of [Mo12E16(PEt3)10] (E = S,Se)

Dodecanuclcar cluster complexes [Mo₁₂S₁₆(PEt₃)₁₀] 1 and [Mo₁₂Se₁₆(PEt₃)₁₀] 2 have been prepared by the reactions of [Mo₆S₈(PEt₃)₆] with sulfur or [Mo₆Se₈(PEt₃)₆] with Cp₂TiSe₅, respectively, in toluene at refluxing temperature. The structures have been determined at 173 K by X-ray crystallography. The compound 1 ·3CHCl₃ crystallizes in the triclinic space group $ {\rm P}\bar 1 $, with a = 14.859(5) Å, b = 15.868(4) Å, c = 14.200(7) Å, α = 100.58(3)°, β = 117.58(3)°, γ = 79.53(2)°, V = 2899(1) ų, and Z = 1. Full-matrix least-squares refinement using 9016 observed reflections (I_o > 2σ(I_o)) gave R = 0.056, and R_w = 0.045. The data for 2 ·2CHCl₃ are: triclinic, $ {\rm P}\bar 1 $, a = 15.737(4) Å, b = 18.763(9) Å, c = 13.062(4) Å, α = 102.45(3)°, β = 128.54(2)°, γ = 69.49(3)°, V = 2825 ų, Z = 1, R = 0.096, and R_w = 0.120 for 5922 reflections (I_o > 2σ(I_o)). The cluster complexes 1 and 2 have two octahedral molybdenum cluster units linked by the rhomboidal intercluster Mo₂(μ₄-E)₂ bonding. The intercluster Mo—Mo distances in 1 are 3.419 Å and 2 3.551 Å. The cyclic voltammetry of 1 and 2 shows two oxidation and two reduction steps separated as large as 380–490 mV. The UV-Vis spectra of the dodecanuclear cluster complexes 1 and 2 have an extra weak band at around 744 nm which is absent in the starting octahedral cluster complexes.     

Stable ‐ESiMe3 Complexes of CuI and AgI (E=S,Se) with NHCs: Synthons in Ternary Nanocluster Assembly

As a part of efforts to prepare new “metallachalcogenolate” precursors and develop their chemistry for the formation of ternary mixed‐metal chalcogenide nanoclusters, two sets of thermally stable, N‐heterocyclic carbene metal–chalcogenolate complexes of the general formula [(IPr)Ag?ESiMe₃] (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene; E=S, 1 ; Se, 2 ) and [(iPr₂‐bimy)Cu?ESiMe₃]₂ (iPr₂‐bimy=1,3‐diisopropylbenzimidazolin‐2‐ylidene; E=S, 4 ; Se, 5 ) are reported. These are prepared from the reaction between the corresponding carbene metal acetate, [(IPr)AgOAc] and [(iPr‐bimy)CuOAc] respectively, and E(SiMe₃)₂ at low temperature. The reaction of [(IPr)Ag?ESiMe₃] 1 with mercury(II) acetate affords the heterometallic complex [{(IPr)AgS}₂Hg] 3 containing two (IPr)Ag?S^? fragments bonded to a central Hg^II, representing a mixed mercury–silver sulfide complex. The reaction of [(iPr₂‐bimy)Cu‐SSiMe₃]₂, which contains a smaller N‐heterocyclic‐carbene, with mercuric(II) acetate affords the high nuclearity cluster, [(iPr₂‐bimy)₆Cu₁₀S₈Hg₃] 6 . The new N‐heterocyclic carbene metal–chalcogenolate complexes 1 , 2 , 4 , 5 and the ternary mixed‐metal chalcogenolate complex 3 and cluster 6 have been characterized by multinuclear NMR spectroscopy (¹H and ¹³C), elemental analysis and single‐crystal X‐ray diffraction.     

Molybdenum(0) and Tungsten(0) Complexes with P,S and P,Se Monooxidized Bis(phosphanyl)amine Ligands

Reactions of monooxidized thioyl and selenoyl bis(phosphanyl)amine ligands C₁₀H₇‐1‐N(P(E)Ph₂)(PPh₂) [E = S ( 1 ), Se ( 2 )] with Mo(CO)₄(pip)₂ and W(CO)₄(cod) afforded the complexes [M(CO)₄{ 1 ‐κ²P,S}] [M = Mo ( 3 ), W ( 4 )] and [M(CO)₄{ 2 ‐κ²P,Se}] [M = Mo ( 5 ), W ( 6 )]. Complexes 3 – 6 were characterized by multinuclear NMR (¹H, ¹³C, ³¹P, and ⁷⁷Se NMR) and IR spectroscopy. Crystal‐structure determinations were carried out on 3 , 5 , and 6 , which represent the first examples of structurally characterized complexes of such ligands with group‐6 metal carbonyls.     

Growth of Sb(2)E(3) (E = S, Se) polygonal tubular crystals via a novel solvent-relief-self-seeding process

A novel solvent-relief-self-seeding (SRSS) process was applied to grow bulk polygonal tubular single crystals of Sb(2)E(3) (E = S, Se), using SbCl(3) and chalcogen elements E (E = S, Se) as the raw materials at 180 degrees C for 7 days in ethanol solution. The products were characterized by various techniques, including X-ray powder diffraction (XRD), scanning electronic microscope (SEM), transmission electronic microscope (TEM), electronic diffraction (ED), and X-ray photoelectron spectra (XPS). The calculated electrical resistivities of the tubular single crystals in the range 20-320 K were of the order of 10(5)-10(6) Omega cm for Sb(2)S(3) and 10(3)-10(4) Omega cm for Sb(2)Se(3), respectively. The studies of the optical properties revealed that the materials formed had a band gap of 1.72 eV for Sb(2)S(3) and 1.82 eV for Sb(2)Se(3), respectively. The optimal reaction conditions for the growth of bulk tubular single crystals were that the temperature was not lower than 180 degrees C and the reaction time was not shorter than 7 days. The possible growth mechanism of tubular crystals was also discussed.     

Gallium and Indium Complexes of Bis(amino thiol) (N(2)S(2)) Ligands

Three methods have been developed to prepare gallium and indium complexes of three tetradentate N(2)S(2) ligands of the general formula M(N(2)S(2))R (M = Ga, In; R = Cl, Br, SCN, O(2)CC(6)H(5)-O,O'). The ancillary ligand (Cl, SCN, O(2)CC(6)H(5)-O,O') was varied with the tetradentate ligand BAT-TM. X-ray crystallography shows that the coordination geometry about the d(10) metal ion is influenced by the steric requirements of the ligands. X-ray crystallography of four molecules results in the following data: GaCl(BAT-TM) (1), formula = C(10)H(22)ClGaN(2)S(2), space group = Pnma, a = 12.387(4) ?, b = 21.116(6) ?, c = 5.986(2) ?, V = 1565.8(9) ?(3), Z = 4; InCl(BAT-TM) (2), formula = C(10)H(22)ClInN(2)S(2), space group = Pnma, a = 12.968(9) ?, b = 29.29(1) ?, c = 5.866(2) ?, V = 1620(2) ?(3), Z = 4; InNCS(BAT-TM) (3), formula = C(11)H(24)ClInN(3)S(3), space group = Pbca, a = 11.812(3) ?, b = 11.679(3) ?, c = 24.238(9) ?, V = 3449.7 (17) ?(3), Z = 8; In(O,O'-O(2)CC(6)H(5))(BAT-TM) (4), formula = C(19)H(29)O(2)InN(2)S(2), space group = P2(1)/n, a = 10.783(2) ?, b = 18.708(4) ?, c = 12.335(4) ?, V = 2321.7(9) ?(3), Z = 4. Proton NMR studies show that the complexes are stable in solution; in polar solvents such as acetonitrile, for certain molecules, two metal-ligand complexes are observed. Similarly, two metal-ligand complexes are seen in NMR data taken in 80% acetonitrile/20% D(2)O (pD = 4.6) mixture. HPLC studies (acetonitrile/50 mM sodium acetate, pH = 4.6) show that the lipophilicity of the ligand determines the retention time of the complex.     

Oxygenation of Co(II) Complexes with Tripodal Ligands

The kinetics of O₂-uptake of five-coordinated Co²⁺/tren complexes (tren = 2,2′, 2″-tris(2-aminoethyl)amine) have been studied extensively. The kinetics of formation of (tren)Co(O₂, OH)Co(tren)³⁺ exhibits two steps. The rate law of O₂-addition, the first step, was of the form: rate = (k[H⁺] + kK_a)/([H⁺] + K_a) [Co(tren)²⁺][O₂]. Second-order rate constants k = 220 ± 19 M ^?1s^?1 and k = 1.8 ± .035 · 10³M ^?1s^?1 agreed well from O₂-uptake and (stopped-flow) spectrophotometric measurements. The protonation constant of the hydroxo complex obtained by equlibrium measurements (spectrophotometric and by pH-titration) in anaerobic conditions (pK_a = 10.03) agreed well with that derived from kinetic data (p K_a = 9.93); k and k are about a factor 100 smaller than those for the pseudooctahedral Co(trien) (H₂O). This and the fact that several other Co(II) complexes with five-coordinated geometry do not exhibit oxygen affinity led to the proposal that the oxygenation mechanism for Co²⁺/tren complexes involves fast preequilibria between Co(tren) (H₂O)²⁺ and Co(tren) (H₂O) and only the latter is assumed to be reactive. The enhanced rate at high pH is explained by rate determining H₂O-exchange in the O₂-addition step and the ability of coordinated OH^? to labilize the neighbouring H₂O. This mechanism is furthermore supported by the formation of one kinetically preferred isomer of the peroxo-bridged dicobalt(III) complex (O₂ cis to the tertiary N-atom) and the large negative activation entropy (?30 eu). The second step is the intramolecular bridging reaction: is independent of [Co(tren)²⁺] and [O₂] but exhibits a pH-dependence of the form k₃ = k′₃[H + ]/(K_a + [H⁺]); k_?3 ( = 5 · 10^?5 s^?1) was determined independently and from the two rate constants the equilibrium constant was calculated as ≈ 10⁵. The ligand combination as in Co(tren)²⁺ was shown to provide an excellent balance to form a reversible oxygen carrier; possible reasons for this are discussed.     

Palladium(II) and Platinum(II) Complexes with Bisphosphanes, [S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Chelating Ligands

The palladium(II) and platin(II) 1, 1‐dicyanoethylene‐2, 2‐dithiolates [(L–L)M{S₂C=C(CN)₂}] (M = Pd: L–L = dppm, dppe, dcpe, dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from[(L–L)MCl₂] and K₂[S₂C=C(CN)₂] or from [(PPh₃)₂M{S₂C=C(CN)₂}] and the bisphosphane. Moreover, [(dppe)Pt{S₂C=C(CN)₂}]was obtained from [(1, 5‐C₈H₁₂)Pt{S₂C=C(CN)₂}] and dppeby ligand exchange. The 1, 1‐dicyanoethylene‐2, 2‐diselenolates[(dppe)M{Se₂C=C(CN)₂}] (M = Pd, Pt) were prepared from[(dppe)MCl₂] and K₂[Se₂C=C(CN)₂]. The oxidation potentials of the square‐planar palladium and platinum complexes were determined by cyclic voltammetry. The reaction of [(dcpe)Pd(S₂C=O)] with TCNE led to a ligand fragment exchange and gave the 1, 1‐dicyanoethylene‐2, 2‐dithiolate [(dcpe)Pd{S₂C=C(CN)₂}] in good yield.     

A New Look at Molecular and Electronic Structure of Homoleptic Diiron(II,II) Complexes with N,N-Bidentate Ligands: Combined Experimental and Theoretical Study

Paddlewheel-type binuclear complexes featuring metal−metal bonding have been the subject of widespread interest due to fundamental concern in their electronic structures and potential applications. Here, we explore the molecular and electronic structures of diiron(II,II) complexes with N,N’-diarylformamidinate ligands. While a paddlewheel-type diiron(II,II) complex with N,N’-diphenylformamidinate ligands (DPhF) exhibits the centrosymmetric [Fe₂(μ-DPhF)₄] structure, a minor alteration in the ligand system, i. e., switching from phenyl to p-tolyl N-substituted formamidinate ligand (DTolF), resulted in the isolation of an unprecedented non-centrosymmetric [Fe(μ-DTolF)₃Fe(κ²-DTolF)] complex. Both complexes were characterized using single-crystal X-ray diffraction, magnetic measurements, ⁵⁷Fe Mössbauer spectroscopy, and cyclic voltammetry along with high-level ab-initio calculations. The results provide a new view on a range of factors controlling the ground-state electronic configuration and structural diversity of homoleptic diiron(II,II) complexes. Model calculations determined that the Mayer bond orders for Fe−Fe interactions are significantly lower than 1 and equal to 0.15 and 0.28 for [Fe₂(μ-DPhF)₄] and [Fe(μ-DTolF)₃Fe(κ²-DTolF)], respectively.     

THE CHEMISTRY OF (ECN)2 (E = S,Se) AND RELATED COMPOUNDS

The psuedohalogens (ECN)₂ (E = S, Se) have been prepared by reaction of AgNCS with bromine and AgNCSe with iodine respectively. (SCN)₂ spontaneously polymerises to give polythiocyanogen a polymer of unknown structure with empirical formula (SCN)_x. A series of late transition metal complexes bearing the ambidentate psuedohalide ligands (ECN) (E = S, Se) have been synthesised. In addition we have prepared a series of late transition metal complexes of the cyanodithioimidocarbonate ion [C₂N₂S₂]^2? and the first transition metal complexes of the cyanodiselenocarbonate ion [C₂N₂Se₂]^2?.     

Electronic Structure of Chalcogen Dichlorides ECl2 (E = S,Se, Te)

The electronic structure of the molecules of chalcogen dichlorides ECl₂ (E = S, Se, Te) was investigated by X-ray spectroscopy and quantum-chemical calculations in the X(SW) approximation. The sequence of the energy levels in the ECl₂ molecules was determined. The nature of the bonding in the various orbitals of the molecules in the SCl₂SeCl₂TeCl₂ series was established. The reasons for the reduced chemical stability of the SeCl₂ molecule and the nonexistence of the TeCl₂ molecule in the individual state are indicated.     

Cationic Ruthenium(II) Carbonyl Complexes with Nitrile Ligands

Stable cationic complexes of the type [RuCO(PPh₃)₂(L)(RCN)]⁺[ClO₄]^? derived from acetonitrile and acrylonitrile have been synthesized. The bidentate ligands (LH) used are acetylacetone, benzoylacetone, dibenzoylmethane, trifluorothenoyl acetone and 8-hydroxyquinoline. The complexes have been characterized by elemental analysis, IR, conductivity, ¹H and ³¹P NMR and ESCA studies, and possible stereochemistry has been established.     

Quantum Chemical Simulation of Hexa-, Penta-, and Tetracoordination Modes in Stereoisomers of the Co(II) and Ni(II) Bis(ligand) Complexes Based on (N,O,S(Se))-Tridentate Azomethines

Russian Journal of Coordination Chemistry - The molecular structures and relative energies of hexa-, penta-, and tetracoordinated stereoisomers of the Co(II) and Ni(II) bis(ligand) complexes based...     

Synthetic applications of (Me3SiNSN)2E (E = S, Se) in chalcogen-nitrogen chemistry: formation and structural characterization of Cl2TeESN2 (E = S, Se) and [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, Br)

The reaction of (Me3SiNSN)2S with TeCl4 in CH2Cl2 affords Cl2TeS2N2 (1) and that of (Me3SiNSN)2Se with TeCl4 produces Cl2TeSeSN2 (2) in good yields. The products were characterized by X-ray crystallography, as well as by NMR and vibrational spectroscopy and EI mass spectrometry. The Raman spectra were assigned by utilizing DFT molecular orbital calculations. The pathway of the formation of five-membered Cl2TeESN2 rings by the reactions of (Me3SiNSN)2E with TeCl4 (E = S, Se) is discussed. The reaction of (Me3SiNSN)2Se with [PPh4]2[Pd2X6] yields [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, 4a; Br, 4b), the first examples of complexes of the (Se2N2S)2- ligand. In both cases, this ligand bridges the two palladium centers through the selenium atoms.