The steric effect of o-tolyl ligand on the fluxionality behavior of some binuclear organoplatinum(II) complexes with bis(diphenylphosphino)methane as bridging ligand

A series of binuclear organoplatinum(II) complexes of general formula cis,cis-[R₂Pt(μ-SMe₂)(μ-dppm)Pt(o-MeC₆H₄)₂], 3a-3d, in which R = Ph, p-MeC₆H₄, m-MeC₆H₄ or p-MeOC₆H₄, were prepared by the reaction of monomeric precursors [Pt(o-MeC₆H₄)₂(dppm)] and cis-[PtR₂(SMe₂)₂]. The binuclear dialkyl analogs, in which R = Me (3e) or R₂ = {(CH₂)₄} (3f), were prepared by the reaction of cis-[Pt(o-MeC₆H₄)₂ (SMe₂)₂] and [PtR₂ (dppm)]. The complexes were fully characterized by multinuclear (¹H, ¹³C, ³¹P, ¹⁹⁵Pt) NMR spectroscopy each as a mixture of syn and anti isomers (depending on the relative orientations of Me substituents on o-tolyl ligands) and each isomer was shown to have a rigid structure. Other binuclear analogs , 3g-3j, in which R is a less steric demanding aryl groups m-MeC₆H₄ or p-MeOC₆H₄, and R′ = Me or , were prepared by the reaction of cis-[PtR₂(SMe₂)₂] and , and shown to have fluxional structures.     

Platinum and rhodium complexes in which diphenylphosphino(methylthio)methane acts as a monodentate,chelated or bridging ligand

Reaction of [PtCl₂(cod)] with Ph₂PCH₂SCH₃ yields cis-[PtCl₂(Ph₂PCH₂-SCH₃)₂] which, on treatment with AgBF₄, is converted to [PtC](Ph₂PCH₂SCH₃)₂]-BF₄, in which one of the ligands is chelated. With [Pt(dba)₂], cis-[Pt(Cl₂(Ph₂PCH₂-SCH₃)₂] reacts to give the platinum(I) complex [Pt₂Cl₂(μ-Ph₂PCH₂SCH₃)₂], which contains a platinum-platinum bond. The terminal chlorides may be replaced by iodide, but the complex is cleaved by carbon monoxide. [Rh₂(μ-Cl)₂(CO)₄] reacts with Ph₂PCH₂SCH₃ to produce [Rh₂Cl₂(CO)₂(μ-Ph₂PCH₂SCH₃)₂], whereas with Ph₂PCH₂CH₂SCH₃ it yields [RhCl(CO)(Ph₂PCH₂CH₂SCH₃)]. A ligand exchange reaction occurs between cis-[PtCl₂(Ph₂SCH₃)₂] and [Rh₂(μ-Cl)₂(CO)₄] to give cis-[PtCl₂(CO)(Ph₂PCH₂SCH₃)] and [Rh₂Cl₂(CO)₂(μ-Ph₂PCH₂SCH₃)₂].     

Cyclometalated platinum(II) complexes containing monodentate phosphines: antiproliferative study

Reaction of cyclometalated platinum(II) precursor [Pt(C^N)Cl(dmso)], 1, C^N = N(1), C(2′)-chelated deprotonated 2-phenylpyridine and dmso = dimethylsulfoxide, with 1 equivalent of triphenyl phosphine, PPh₃, or 1,3,5-triaza-7-phosphaadamantane, PTA, gave the complex [Pt(C^N)Cl(PPh₃)], 2, or [Pt(C^N)Cl(PTA)], 3, respectively. On the basis of careful multinuclear NMR spectroscopy, supported by a number of 2D NMR experiments, structures of the complexes 2 and 3 in solution were determined to be neutral four coordinate. The X-ray crystallography indicated that the solid-state structure of complex 3 comprised a common square-planar geometry around platinum(II). Cytotoxicity of the complexes 2 and 3 was studied in three human cancer cell lines derived from ovarian carcinoma (CH1), lung carcinoma (A549), and colon carcinoma (SW480).     

Cyclometalated ruthenium(II) complexes with a bis-carbene CCC-pincer ligand

The first series of cyclometalated ruthenium complexes with a CCC-pincer bis-carbene ligand have been obtained as bench-stable compounds. Single-crystal X-ray analysis of one of these complexes with 4'-di-p-anisylamino-2,2':6',2'-terpyridine is presented. The Ru(II/III) redox potentials and MLCT absorptions of these complexes can be varied by attaching an electron-donating or -withdrawing group on the noncyclometalating ligand.     

Synthesis and Structure of Di［bis（diphenylphosphino）ethane］ Copper（Ⅱ） Dinitrate

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Binuclear nickel(II) complexes with a bridging carbonato ligand

Three nickel(II) dinuclear carbonato-bridged complexes: (-CO3)[Ni(TAA)]2(ClO4)2·4H2O (1), (-CO3)[Ni(TTA)]2- (ClO4)2·2H2O (2), (-CO3)[Ni(cyclam)]2(ClO4)2 (3) [TAA =N(CH2CH2NH2)3,TTA=triethylenetetramine,cyclam = 1,4,8,11-tetraazacyclotetradecane] have been prepared. The temperature dependence of the magnetic susceptibility for (1), (2) and (3) were measured over the 77–300K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator (H= –2JS1S2), giving the exchange integral J=–7.75cm–1 for (1), J=–1.23 cm–1 for (2) and J=–40.26cm–1 for (3).     

Synthesis and properties of the chain-like polymeric copper (II) complexes bridged by bis(diphenylphosphino oxide)ethane

At room temperature, the chain-like polymeric copper (II) complexes bridged by bis (diphenylphosphino oxide) ethane (dppeO2), [Cu(dppeO2)X2]n[X=Cl(1), Br(2)] have been prepared and characterized by elemental analysis, 31P NMR, TG-DTA and X-ray analysis for [ CuBr2 (dppeO2) ] n The chain is composed of subunits containing tetrahedron coordinated copper (II) atoms. The four-coordinated copper (II) atom is ligated to another four-coordinated copper (II) atom through dppeO2. The coordination sphere of copper(II) atom is completed by two monodentate bromide and two oxygen atoms from bridging dppeO2. Crystal data are as follows: C26-H24CuP2BnO2, 0.50 mm× 0.40 mm×0.40 mm, monoclin-ic, space group: C2/c, λ= 0.07107 nm(Mo Ka), a = 1.2286(2) nm, b=2.0555(8) nm, c = 1.0652(2) nm, β = 97.366(9)°, V = 2.668nm3, Z = 4, Dcalc = 1.628 g·cm-3, R = 0.066; Rw = 0.091.     

Blue electrophosphorescent organoplatinum(II) complexes with dianionic tetradentate bis(carbene) ligands

Robust charge-neutral Pt(II) complexes containing dianionic tetradentate bis(N-heterocyclic carbene) ligands exhibit intense blue phosphorescence in fluid solutions and in polymer films, and have been vacuum-deposited as a phosphorescent dopant in organic blue-light-emitting diodes.     

Silver(I) complexes of bis[2-(diphenylphosphino)phenyl] ether

The reaction of AgOTf in dichloromethane with bis(2-(diphenylphosphino)phenyl) ether (DPEphos) in an equimolar ratio afforded a dinuclear complex [Ag₂(κ²-P,P′-DPEphos)₂(μ-OTf)₂] (1), whereas the similar reaction in a 1:2 molar ratio resulted in the formation of a bis-chelating complex [Ag(κ²-P,P′-DPEphos)₂][OTf] (2). The silver(I) complex 1 was obtained as a dimer, in which two silver atoms are bridged by two triflate groups to form three adjacent eight-membered spirocyclic rings. The mixed-ligand complex [Ag(κ²-P,P′-DPEphos)(2,2′-bpy)][OTf] (3) was obtained in the reaction of 1 in dichloromethane with 2,2′-bipyridine. The crystal structures of complexes 1–3 were determined by single crystal X-ray analyses.     

Synthesis and properties of Zr-Co heterodinuclear complexes with a bridging bis(cyclopentadienyl) ligand

[(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(C₅H₅)] reacted with Co₂(CO)₈ to produce a heterodinuclear Zr(IV)-Co(I) complex [(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(η⁵-C₅H₄)Co(CO)₂] (3). Complex 3 underwent oxidative addition of I₂ to give [(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(η⁵-C₅H₄)CoI₂(CO)] (4) having Zr(IV) and Co(III) centers. The carbonyl ligand of 4 was easily replaced with P(OMe)₃ and PPh₃ to afford [(η⁵-C₅H₅)ZrCl₂(η⁵-C₅H₄)CMe₂(η⁵-C₅H₄)CoI₂(L)] (5: L = P(OMe)₃, 6: L = PPh₃). Structures of 5 and 6 were determined by X-ray crystallography. These Zr-Co heterodinuclear complexes catalyzed polymerization of ethylene and propylene.     

Deprotonated bis(diphenylphosphino)methane as a monodentate C-bonded ligand: preparation and 31P/199Hg NMR characterisation of Hg[CH(PPh2)2]2

HgCl₂ reacts with 2 equivalents of (PPh₂)₂CHLi to yield the title compound. The deprotonated dppm ligands are monodentate and bonded through the methine carbon atoms as shown by ³¹P and ¹⁹⁹Hg NMR spectroscopy.     

Synthesis and photophysical properties of complexes of Be(II) and Zn(II) with 10-hydroxybenzo[h]quinoline ligand

Two 10-hydroxybenzo[h]quinoline metal complexes, bis(10-hydroxybenzo[h]quinolinato) beryllium (Bebq2) and bis(10-hydroxybenzo[h]quinolinato)zincum (Znbq2), have been synthesized. The structure are characterized by 1HNMR, IR and so on. The photophysical processes of Bebq2 and Znbq2 have been carefully investigated by fluorescence spectra. The results show that the compounds emit yellow-green and yellow light. The emission peaks are at 492 and 512 nm, respectively. In addition, the light-emitting can be quenched by electron donor, N,N-dimethylaniline (DMA), and the quenching process follows the Stern-Volmer equation. Furthermore, the molecular interactions of Bebq2 and Znbq2 with electron acceptor, dimethylterephthalate (DMTP), were also carefully investigated. It displayed that the Znbq2 is a potential substitute for Bebq2 as an excellent emitting material.