Two novel Keggin tungstocobaltates grafted by cobaltII complex group(s): K[Co(phen)2(H2O)]2[HCoW12O40]·2H2O and [Co(2,2′-bipy)3]1.5{[Co(2,2′-bipy)2(H2O)][HCoW12O40]}·0.5H2O

Two novel inorganic–organic hybrid compounds composed of Keggin tungstocobaltate framework and cobalt(II)–N coordination complexes, K[Co(phen)₂(H₂O)]₂[HCoW₁₂O₄₀]·2H₂O (1) (phen = 1,10-phenanthroline) and [Co(2,2′-bipy)₃]_1.5{[Co(2,2′-bipy)₂(H₂O)][HCoW₁₂O₄₀]·0.5H₂O (2) (bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Keggin POMs as starting materials, which were characterized by elemental analyses, IR, TG analyses and X-ray single crystal diffraction. Crystal data for compound 1: C₄₈H₄₁Co₃KN₈O₄₄W_12, triclinic, space group P-1, a = 10.918(5) Å, b = 13.401(5) Å, c = 13.693(5) Å, α = 69.291(5)°, β = 71.568(5)°, γ = 78.421(5)°, V = 1768.9(12) Å³, Z = 1; for compound 2: C₁₃₀H₁₀₄Co₇N₂₆O₈₃W_24, orthorhombic, space group, C2/c, a = 46.839(9) Å, b = 14.347(3) Å, c = 26.147(5) Å, α = β = γ = 90°, V = 17,570(6) Å³, Z = 4. Compound 1 exhibits a pseudo-1D chainlike structure, in which potassium ions act as linkages of Keggin unit doubly grafted by [Co(phen)₂(H₂O)] complex. Compound 2 represents a [Co(2,2′-bipy)₂(H₂O)]²⁺ mono-grafted Keggin tungstocobaltate derivative with 1.5[Co(2,2′-bipy)₃]²⁺ countercations. The cyclic voltammetric behavior of 1-CPE is similar to the parent 3-CPE, but the cyclic voltammetric behavior of Co^II shows a little difference. Variable-temperature magnetic susceptibility measurement of compound 1 demonstrates the presence of antiferromagnetic interactions.     

Two coordination polymers of manganese(II) isophthalate and their preparation,structures, and magnetic properties

Two manganese coordination polymers, [Mn₂(ip)₂(dmf)]·dmf (1) and [Mn₄(ip)₄(dmf)₆]·2dmf (2) (ip=isophthalate; dmf=N,N-dimethylformamide), have been synthesized and characterized. X-ray crystal structural data reveal that compound 1 crystallizes in triclinic space group P?1, a=9.716(3) Å, b=12.193(3) Å, c=12.576(3) Å, α=62.19(2)°, β=66.423(17)°, γ=72.72(2)°, Z=2, while compound 2 crystallizes in monoclinic space group Cc, a=19.80(3) Å, b=20.20(2) Å, c=18.01(3) Å, β=108.40(4)°, Z=4. Variable-temperature magnetic susceptibilities of compounds 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions.     

Synthesis,spectroscopic studies and structures of square-planar nickel(II) and copper(II) complexes derived from 2-{(Z)-[furan-2-ylmethyl]imino]methyl}-6-methoxyphenol

Two new nickel(II) [Ni(L)₂] and copper(II) [Cu(L)₂] complexes have been synthesized with bidentate NO donor Schiff base ligand (2-{(Z)-[furan-2-ylmethyl]imino]methyl}-6-methoxyphenol) (HL) and both complexes Ni(L)₂ and Cu(L)₂ have been characterized by elemental analyses, IR, UV–vis, ¹H, ¹³C NMR, mass spectroscopy and room temperature magnetic susceptibility measurement. The tautomeric equilibria (phenol-imine, O–H?N and keto-amine, O?H–N forms) have been systemetically studied by using UV–vis absorption spectra for the ligand HL. The UV–vis spectra of this ligand HL were recorded and commented in polar, non-polar, acidic and basic media. The crystal structures of these complexes have also been determined by using X-ray crystallographic techniques. The complexes Ni(L)₂ and Cu(L)₂ crystallize in the monoclinic space group P2₁/n and P2₁/c with unit cell parameters: a = 10.4552(3) Å and 12.1667(4) Å, b = 8.0121(3) Å and 10.4792(3) Å, c = 13.9625(4) Å and 129.6616(3)Å, V = 1155.22(6) Å³ and 1155.22(6) Å³, D_x = 1.493 and 1.476 g cm^?3 and Z = 2 and 2, respectively. The crystal structures were solved by direct methods and refined by full-matrix least squares to a find R = 0.0377 and 0.0336 of for 2340 and 2402 observed reflections, respectively.     

Synthesis and structure of a new scorpionate-dithio carboxyl oxovanadium complex and an organic dithio carboxyl compound

A new complex of oxovanadium(IV), V₂O₂[(HB(pz)₃)₂(pyrro)₂ (1) and a dimer-dithio carboxyl compound (C₅H₈NS₂)₂ (2) have been synthesized by the reaction of VOSO₄·nH₂O with NaHB(pz)₃ and pyrrolidine dithio carboxylic acid ammonium salt. They were characterized by element analysis, IR spectra, UV–vis spectra and X-ray diffraction. Structural analyses of 1 and 2 gave the following parameters: 1, triclinic, P-1, a = 7.732(4) Å, b = 14.285(8) Å, c = 17.802(9) Å, α = 101.314(8)°, β = 92.682(9)°, γ = 92.228(9)°, V = 1923.6(18) Å³, and Z = 4; 2, monoclinic, C2/c, a = 13.857(2) Å, b = 10.4213(18) Å, c = 9.436(2) Å, β = 97.099(2), V = 1352.1(4) Å³, and Z = 4. In complex 1, vanadium atom adopts a distorted tetragonal bipyramid structure, which is typical for oxovanadium(IV) complexes. Compound 2 is a dimer-dithio carboxyl compound with S–S bond. In addition, thermal analysis was performed for analyzing the stabilization of the complexes.     

Copper(II)-methylmalonate complexes with unidentate N-donor ligands: Syntheses,structural characterization and magnetic properties

Two new methylmalonate-bridged copper(II) complexes with the formulas [Cu(3-Ipy)(Memal)(H₂O)] (1) and [Cu(2,4′-bpy)(Memal)(H₂O)] · 3H₂O (2) [Memal = methylmalonate dianion, 3-Ipy = 3-iodopyridine, 2,4′-bpy = 2,4′-bipyridine] have been synthesized and characterized by X-ray diffraction. Both compounds crystallize in the monoclinic space group P2₁/n and Z = 4, with unit cell parameters a = 8.5874(13) Å, b = 7.1738(14) Å, c = 19.093(5) Å, β = 99.509(15)° in 1 and a = 17.375(4) Å, b = 7.3305(14) Å, c = 14.247(3) Å, β = 111.409(15)° in 2. The structures of 1 and 2 consist of zigzag chains of anti-syn carboxylate-bridged copper(II) ions running along the b direction. The pyridine-like ligands occupy one equatorial position of the copper environment avoiding the formation of the sheet-like arrangement observed in previously reported Memal complexes. The chains are grouped together in hydrophilic layers through hydrogen bonds and the layers are pillared through the 3-Ipy (1) and 2,4′-bpy (2) ligands which are stacked through π–π interactions involving alternatively aromatic ligands from two adjacent chains. Magnetic susceptibility measurements of both compounds in the temperature range 2–290 K show the occurrence of intrachain ferromagnetic interactions between the copper(II) ions [J = +2.66(2) cm^?1 (1) and J = +2.62(2) cm^?1 (2)].     

New metastable hybrid phase,Zn2(OH)2(C8H4O4), exhibiting unique oxo-penta-coordinated Zn(II) atoms

The metastable phase (phase 1) Zn(OH)₂(tp)₂ (tp = C₈H₄O₄^2?) was found to be an intermediate forming during the hydrothermal synthesis of Zn₃(OH)₄tp (phase 2). Its structure has been determined ab initio from synchrotron powder diffraction data and refined with the Rietveld method: space group P2₁/c, a = 3.48856(2) Å, b = 5.84645(2) Å, c = 22.1331(1) Å, β = 103.46(1)°, D_x = 2.488 g/cm³, R_p = 0.10, R_B = 0.095 (402 independent reflections). The structures of the two analogues were compared. Whereas a mixed coordination of the zinc atoms was found in phase 2, phase 1 exhibits only penta-coordinated Zn(II). Moreover, different optical properties were observed, Zn₂(OH)₂(tp) showing photoluminescence at 378 nm under λ_ex = 316 nm.     

Copper and cadmium phosphonates based on 2-quinolinephosphonate

Hydrothermal reactions of 2-quinolinephosphonic acid (1) and CuSO₄ or CdSO₄ result in two new compounds with formula Cu(2-C₉H₆NPO₃) (2) and Cd(2-C₉H₆NPO₃)(H₂O) (3). Compound 2 has a layer structure in which dimers of edge-sharing {CuO₄N} square-pyramids are linked by {CPO₃} tetrahedra through corner sharing. Compound 3 shows a new type of layer structure where chains of corner sharing {CdO₅N} octahedra are connected by {CPO₃} tetrahedra into an inorganic layer. The quinoline groups fill in the inter-layer spaces in both cases. Crystal data for 1: monoclinic, space group P2₁/c, a = 10.270(2) Å, b = 13.566(3) Å, c = 6.9818(16) Å, β = 101.916(4)°, V = 951.8(4) Å³, Z = 4. For 2: monoclinic, space group P2₁/c, a = 13.976(3) Å, b = 7.9398(18) Å, c = 7.8687(18) Å, β = 101.150(5)°, V = 856.7(3) Å³, Z = 4. For 3: monoclinic, space group P2₁/c, a = 17.164(4) Å, b = 5.4870(12) Å, c = 10.850(2) Å, β = 101.557(4)°, V = 1001.1(4) Å³, Z = 4. The magnetic measurement on 2 reveals a dominant antiferromagnetic exchange coupling between the Cu(II) centers. A quasi-reversible electrochemical reaction is observed for complex 2 immobilized on the surface of GC electrode, corresponding to the redox couple Cu²⁺/Cu⁺. The fluorescent properties of 1–3 are also investigated.     

Organic derivatives of tin (II/IV): Investigation of their structure

The structures of tin(II)-oxalate, tin(IV)Na–EDTA and tin(IV)Na₈-inositol hexaphosphate were investigated using XRD analysis. Samples were identified using the Mössbauer study, thermal analysis and FTIR spectrometry. The Mössbauer study determined two different oxidation states of tin atoms, and consequently two different tin surroundings in the end products. The tin oxalate was found to be orthorhombic with space group Pnma, a=9.2066(3) Å, b=9.7590(1) Å, c=13.1848(5) Å, V=1184.62 Å³ and Z=8. SnNa–EDTA was found to be monoclinic with space group P2₁/c₁, a=10.7544(3) Å, b=10.1455(3) Å, c=16.5130(6) Å, β=98.59(2)°, V=1781.50(4) Å³ and Z=4. Sn(C₆H₆Na₈O₂₄P₆) was found to be amorphous.     

Synthesis,crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa = hexafluoroacetylacetonate,Phen = o-phenanthroline)

The mixed ligand complex [La(hfa)₃(Phen)₂] (I) was obtained by the interaction of La(hfa)₃ and Phen; its composition does not depend on the stoichiometry of the reagents. According to the X-ray single crystal analysis data, complex I crystallizes in the monoclinic space group P2₁/n, with a = 13.583(3) Å, b = 16.959(3) Å, c = 18.860(4) Å, β = 94.71(3)° and Z = 4. The structure of I consists of isolated mononuclear molecules, the coordination number of La being 10. Thermal behaviour and composition of the vapor phase have been studied for I by thermal analysis and mass-spectrometry using a Knudsen cell. The mixed ligand complex I was found to sublime congruently in the temperature range 370–460 K: [La(hfa)₃(Phen)₂]_(s) = [La(hfa)₃(Phen)]_(g) + Phen_(g), Δ_rH⁰(T) = 316.2 ± 1.8 kJ/mol.     

Synthesis and structural characterization of a photoresponsive organodirhodium complex with active S–S bonds: [(CpPhRh)2(μ-CH2)2(μ-O2SSO2)] (CpPh = η5-C5Me4Ph)

A photoresponsive rhodium dinuclear complex having phenyltetramethylcyclopentadienyl (Cp^Ph = η⁵-C₅Me₄Ph) and photosensitive dithionite (μ-O₂SSO₂) ligands, [(Cp^PhRh)₂(μ-CH₂)₂(μ-O₂SSO₂)] (1), has been synthesized. The crystal of complex 1 (monoclinic, C2/m (No. 12), a = 24.805(2) Å, b = 29.111(2) Å, c = 10.8475(11) Å, β = 105.9830(7)°, V = 7530.0(12) Å³, Z = 8) consists of two independent molecules, 1-cis and 1-trans, with different arrangement of the Cp^Ph ligands. The flexibility, volume, and shape of the reaction cavities around the dithionite unit of 1-cis and 1-trans in the crystal are discussed. The crystal structures of the precursors of 1, trans-[(Cp^PhRh)₂(μ-Cl)₂Cl₂] and trans-[(Cp^PhRh)₂(μ-CH₂)₂Me₂], are also reported.     

Syntheses,structures and single-molecule magnetic behaviors of two dicubane Mn4 complexes

The reaction of MnX₂ · 4H₂O (X = Cl or Br) with 2,6-bis(hydroxymethyl)-4-methylphenol (H₃L) and NaOH in methanol solution yielded two tetranuclear manganese complexes, [Mn₄(HL)₄(MeOH)₄Cl₂] (1) and [Mn₄(HL)₄(MeOH)₄Br₂] (2). Both compounds crystallize in the monoclinic space group C₂/c with cell parameters: a = 26.0945(19) Å, b = 11.4999(8) Å, c = 21.2188(16) Å, β = 121.050(1)° and z = 4 for 1 · 2Et₂O; a = 25.8145(3) Å, b = 11.6734(2) Å, c = 21.3956(3) Å, β = 120.1277(6)° and z = 4 for 2 · 2Et₂O. Both complexes consist of a mixed-valence dicubane structure, which comprises two Mn^II and two Mn^III ions. Magnetic susceptibilities and magnetization of complexes 1 and 2 in the solid state indicate that two clusters have an S = 9 ground state. Frequency-dependent out-of-phase signals of alternating current magnetic susceptibilities were observed in the low temperature range (<3 K) for both complexes indicating a slow magnetic relaxation.     

New transition metal sulfates templated by 1,4-butanediamine, (C4H14N2)[MII(H2O)6](SO4)2·4H2O (MII: Co,Ni): Structure,reactivity and thermal decomposition

Two new hybrid materials, (C₄H₁₄N₂)[M^II(H₂O)₆](SO₄)₂·4H₂O (M^II: Co (I), Ni (II)), have been synthesised by slow evaporation method at room temperature and crystallographically characterized. They crystallise isotypically in the monoclinic system, space group P2₁/n, with the following unit-cell parameters a = 9.2285(3), b = 11.3333(4), c = 10.6693(4) Å, β = 109.004(2)°, Z = 2 and V = 1055.07(6) Å³ for I and a = 9.2127(2), b = 11.3182(2), c = 10.6434(2) Å, β = 109.094(1)°, Z = 2 and V = 1048.74(4) Å³ for II. The structure of the two supramolecular compounds consists of metallic cation octahedrally coordinated to six water molecules, sulfate anions, 1,4-butanediammonium cation and water molecules linked together via two types of hydrogen bonds, O–H?O and N–H?O. The two compounds are not stable at room temperature and their partial dehydration depends on the humidity of the environment. The thermal decomposition of precursors, studied by thermogravimetric analysis (TG) and temperature-dependent X-ray diffraction (TDXD), shows successive intermediate hydrates and crystalline anhydrous compounds upon dehydration.     

Ce(H2O)(PO4)3/2(H3O)1/2(H2O)1/2, a second entry in the structural chemistry of cerium(IV) phosphates

A cerium(IV) phosphate has been prepared using precipitation methods and its structure has been solved by single crystal X-ray diffraction (R₁ = 0.0292 for 3092 reflections with I>2σ(I) and wR₂ = 0.0540). Ce(H₂O)(PO₄)_3/2(H₃O)_1/2(H₂O)_1/2 crystallises in the monoclinic space group C2/c (a = 15.7058(17) Å, b = 9.6261(9) Å, c = 10.1632(4) Å, ß = 121.623(7)°, and V = 1308.4 (2) Å³). Its structure is based on a negatively charged 3D framework, made of cerium atoms connected by PO₄ tetrahedra. There are two types of PO₄ units; one shares only corners with the cerium coordination polyhedra while the other one shares edges and corners. This structure also includes hydronium cations, to balance the framework charge, and water molecules. One special feature of this 3D framework is the formation of interconnected tunnels which extend along the c axis and contain the hydronium cations and the water molecules. This open framework and the presence of cationic species in the tunnels are in perfect agreement with the previously reported ion exchange properties.     

Hybrid inorganic–organic frameworks containing magnesium: Synthesis and structures of magnesium squarate,diglycolate, and glutarate,and potassium magnesium cyclobutanetetracarboxylate

Four new magnesium containing metal–organic hybrid compounds have been synthesized in an effort to prepare low-density materials for hydrogen storage. The compounds were prepared hydrothermally and characterized using single crystal X-ray diffraction. Three of these compounds are analogs of known transition metal structures with squarate (I, Pn-3n, a = 16.276(5) Å), diglycolate (II, P2₁2₁2₁, a = 6.860(1) Å, b = 9.993(1) Å, c = 10.884(1) Å, R₁ = 0.0341), and glutarate (III, R-3, a = 10.744(2) Å, c = 28.677(5) Å, R₁ = 0.0554) ligands; the fourth is a novel structure using cyclobutanetetracarboxylate (IV, Pccn, a = 9.382(1) Å, b = 14.410(2) Å, c = 8.725(1) Å, R₁ = 0.0465) which contains potassium as well as magnesium cations.     

Synthesis,structure and property of a new inorganic–organic hybrid compound [Cu(phen)2][Cu(phen)H2O]2[Mo5P2O23]·3.5H2O

A new polyoxomolybdophosphate 1, formulated as [Cu(phen)₂][Cu(phen)H₂O]₂[Mo₅P₂O₂₃]·3.5H₂O (phen = 1,10-phenanthroline) has been synthesized under hydrothermal conditions. Compound 1 crystallizes in the triclinic space group P-1 with a = 12.2429(5) Å, b = 14.3543(5) Å, c = 20.0814(8) Å, α = 80.023 (1)°, β = 74.283 (1)°, γ = 66.452(1)°, V = 3105.8(2) Å³, R₁ = 0.0375, wR₂ = 0.0885, Z = 2 and GOF = 1.009. Compound 1 is constructed from diphosphopentamolybdate clusters coordinated to Cu(II)-phen units, and free water molecules, which are connected to a three-dimensional framework via π–π stacking interactions from the phen ligands. The single-crystal X-ray diffraction, FT-IR, TG-DTA, XPS, EPR and fluorescent spectra for this compound were determined. The electrochemical properties of compound 1 are studied using cyclic voltammogram, the results indicated that the compound 1 shows good electrocatalytic activity to NO₂^?.     

Two fumarato-bridged Co(II) coordination polymers: syntheses,crystal structures and properties of Co(H2O)4L and [Co3(H2O)4(OH)2L2]·2H2O with H2LHOOCCHCHCOOH

Two fumarato-bridged Co(II) coordination polymers Co(H₂O)₄L 1 and [Co₃(H₂O)₄(OH)₂L₂]·2H₂O 2 with H₂LHOOCCH CHCOOH were prepared. Complex 1 consists of polymeric chains _∞¹[Co(H₂O)₄(C₄H₂O₄)_2/2], which result from octahedrally coordinated Co atoms bridged by bis-monodentate fumarate anions and are assembled by interchain hydrogen bonds. Within 2, the edge-shared Co₂O₁₀ bi-octahedra are connected to the CoO₆ octahedra to form 1D cobalt oxide chains and 3D open framework generated from the chains inter-linked by bis-bidentate fumarate anions displays rhombic tunnels, which are filled with the lattice H₂O molecules. Thermal and magnetic behaviors of both the title coordination polymers are discussed. Crystal data: (1) monoclinic, P2₁/c, Z=4, a=7.493(1) Å, b=14.377(1) Å, c=7.708(1) Å, β=99.54(1)°, V=818.9(2) Å³, R₁=0.0304, and wR₂=0.0669 for 1487 observed reflections (I⩾2σ(I)) out of 1877 unique reflections; (2) monoclinic, P2₁/c, Z=2, a=6.618(1) Å, b=8.172(2) Å, c=15.578(3) Å, β=96.30(3)°, V=837.4(3) Å³, R₁=0.0360 and wR₂=0.0663 for 1442 observed reflections (I⩾2σ(I)) out of 1927 unique reflections.     

Synthesis and structure of a bimetallic hybrid inorganic/organic layered coordination polymer with an octamolybdate cluster variant trapped between the α and δ isomeric forms

Hydrothermal combination of CuSO₄, MoO₃, and 4-phenylpyridine (4-phpyr) in a 1:4:4.5 ratio under basic conditions afforded purple crystals of {[Cu(4-phpyr)₄]₂(Mo₈O₂₆)·4-phpyr} (1), which were analyzed by spectroscopy and single crystal X-ray diffraction. The asymmetric octamolybdate clusters in 1 adopt an intermediate structural variant between the known α and δ isomeric forms, with four octahedral and three tetrahedral molybdenum coordination spheres, along with one molybdenum atom in a highly distorted square pyramidal environment. Paddle-wheel shaped [Cu(4-phpyr)₄]²⁺ cations link adjacent {α/δ-Mo₈O₂₆}⁴⁻ clusters into a 2-D layered rhomboid grid coordination polymer. Uncoordinated 4-phpyr molecules lie in incipient voids in the interlamellar regions. The structure of 1 illustrates the utility of sterically bulky coordination complexes in the stabilization of intermediate conformations during energetically facile polyoxometallate isomer interconversion. Crystallographic data: triclinic, P1, a = 13.717(3) Å, b = 13.728(3) Å, c = 14.809(3) Å, α = 109.251(4)°, β = 107.670(4)°, γ = 92.005(4)°, V = 2480.0(9) Å³, R₁ = 0.0637, wR₂ = 0.1054.     

Syntheses and crystal structures of new vanadium(IV) oxyphosphates M(VO)2(PO4)2 with M = Co,Ni

We have extended our research interest on titanium oxyphosphates (M^II(TiO)₂(PO₄)₂, with M^II = Mg, Fe, Co, Ni, Cu, Zn) to vanadium oxyphosphates M^II(V^IVO)₂(PO₄)₂ (M^II = Co, Ni). For each compound two phases, named α and β according to synthesis conditions, have been stabilized at room temperature, then characterized. The four crystal structures M(VO)₂(PO₄)₂ (α and β for M = Co, Ni) have been determined in monoclinic P2₁/c space group using X-ray single crystals diffraction data. Structure of the α phase is derived from the Li(TiO)(PO₄) (orthorhombic Pnma) and LiNi_0.50(TiO)₂(PO₄)₂ (monoclinic P2₁/c) types, with cell parameters: a = 6.310(1) Å, b = 7.273(1) Å, c = 7.432(1) Å, β = 90.43(1)° for M = Co, and a = 6.297(2) Å, b = 7.230(2) Å, c = 7.421(2) Å, β = 90.36(2)° for M = Ni. Structure of the β phase is derived from the Ni(TiO)₂(PO₄)₂-type (monoclinic P2₁/c) with cell parameters: a = 7.2742(2) Å, b = 7.2802(2) Å, c = 7.4550(2) Å, β = 120.171(2)° for M = Co, and a = 7.2691(2) Å, b = 7.2366(2) Å, c = 7.4453(2) Å, β = 120.231(2)° for M = Ni. All these structures consist of a three dimensional (3D) framework built up of infinite chains of tilted corner-sharing [VO₆] octahedra, cross-linked by corner-sharing [PO₄] tetrahedra. The M²⁺ ion (M = Co, Ni) is located in a triangular based antiprism which shares faces with two [VO₆] octahedra. Structural filiation is discussed based on a common structural unit, a sheet where divalent cations M²⁺ (M = Co, Ni) are inserted. A thermal study of the α ? β transition is also presented.     

Dialkyl- and diaryl-platinum(II) complexes with secondary phosphines: Preparation,structure and thermal reaction giving the metallopolymer

Alkyl and arylplatinum complexes with 1,5-cyclooctadiene ligand, [PtR₂(cod)] (R = Me, Ph, C₆H₄-p-CF₃, C₆F₅), react with secondary phosphines, PHR′₂ (R′ = i-Bu, t-Bu, Ph), to afford the mononuclear platinum complexes, cis-[PtR₂(PHR′₂)₂] (1a: R = Me, R′ = i-Bu; 1b: R = Me, R′ = t-Bu; 1c: R = Me, R′ = Ph; 2a: R = Ph, R′ = i-Bu; 2b: R = Ph, R′ = t-Bu; 2c: R = R′ = Ph; 3a: R = C₆H₄-p-CF₃, R′ = i-Bu; 3b: R = C₆H₄-p-CF₃, R′ = t-Bu; 3c: R = C₆H₄-p-CF₃, R′ = Ph; 4a: R = C₆F₅, R′ = i-Bu; 4c: R = C₆F₅, R′ = Ph) in 81–98% yields. Molecular structures of the complexes except for 1a, 1c and 2a were determined by X-ray crystallography. Complex 1b has a square-planar structure with Pt–C(methyl) bonds of 2.083(8) and 2.109(8) Å, while the Pt–C(aryl) bonds of 2b–c, 3a–c, 4a and 4c (2.055(1)–2.073(8) Å) are shorter than them. Thermal decomposition of 1b, 2a–c, and 3a–c releases methane, biphenyl or 4,4′-bis(trifluoromethyl)biphenyl as the organic products, which are characterized by NMR spectroscopy. The solid product of the thermal reactions of 2b and 2c were characterized as the metallopolymers formulated as [Pt(PR′₂)₂]_n (5b: R′ = ^tBu; 5c: R′ = Ph), based on the solid-state NMR and elemental analyses.