Reactions of Bis(Trifluoromethyl)Phosphine and Tetrakis(Trifluoromethyl)Phosphine with Ruthenium Carbonyl Clusters

Abstract

The reaction of (CF₃)₂P-P(CF₃)₂ with [Ru₃(CO)₁₂] yielded compounds : [Ru₁₄(CO)₁₃{μ-P(CF₃)₂)₂] (1), [Ru₄(CO)₁₄{μ-P(CF₃)₂}₂] (2), and [Ru₄(CO)₁₁{μ-P(CF₃)₂}₄] (3); reaction with [μ-H)₄Ru₄(CO)₁₂] yielded (1) and [(μ-H)₃Ru₄(CO)₁₂{μ-P(CF₃)₂}] (4). The reaction of (CF₃)₂PH with [Ru₃(CO)₁₂] yielded compounds (1) and (4) and compounds (1) and (2) using cluster : ligand ratios of 1:1 and 1:2 respectively. All the compounds have been characterised by X-ray crystallography; a schematic diagram of their structures is shown in Figure 1. The fluxional behaviour of the hydrides in (4) was studied using variable temperature ¹H NMR spectroscopy (see Figure 2). The result of this study was used in the assignment of hydride positions of (4) in the solid state.     

A series of Keggin-based AgI-belt/cycle structures constructed from 5-phenyl-1H-tetrazole and its derivative through Ag–N and Ag–C bonds

Three Keggin-based compounds containing Ag^I belts and cycles constructed from 5-phenyl-1H-tetrazole (L¹) and its derivative 5-m-tolyl-1H-tetrazole (L²), [Ag₉L¹₅(PW^VW^VI₁₁O₄₀)]·H₂O (1), [Ag₁₁L¹₆(H₂O)₂(SiMo^VMo^VI₁₁O₄₀)] (2) and [Ag₁₀L²₈(HPMo₁₂O₄₀)]·H₂O (3), have been synthesized under hydrothermal conditions and characterized by IR spectra and single crystal X-ray diffraction. Compound 1 shows a channel-like 3-D metal-organic framework with Keggin anions in channels. Adjacent layers of 2 share the same anions to construct a 3-D framework. Compound 3 has a 2-D metal-organic layer containing Ag^I cycles. Adjacent layers link through sharing Ag–N bonds and a channel-like 3-D framework is formed. Electrochemical and photocatalytic properties of 1–3 have been studied. The experimental results show that 1–3 have excellent catalytic performance for reduction of nitrite and bromate and also have photocatalytic properties for degradation of MB and RhB.     

Syntheses,structures, and luminescence of two Zn(II) coordination polymers based on 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole and carboxylates

Reactions of Zn(II) salts, 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and 2-mercaptobenzoic acid or 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H₃PrIDC), result in two mixed-ligand coordination polymers (CPs), [Zn₂(IPT)(DSDB)(OH)]_n (H₂DSDB = 2,2′-disulfanediyldibenzoic acid, 1) and [Zn₂(IPT)(PrIDC)(H₂O)]_n (H₃PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2). Compound 1 possesses a 2-D structure built by 1-D [Zn(IPT)]_n chains and DSDB^2? connectors, in which the DSDB^2? is generated via in situ reaction from 2-mercaptobenzoic acid. It displays a new intricate 4-nodal {3·4·6·7·8·9}{3·6·7·8·9·10}{3·8·9}{4·6·8} topology. Compound 2 displays a 3-D framework with new 3-connected topology with Schläfli symbol of (4·8·10) (8·12²), in which the 1-D Zn-carboxylate chains were bridged by 3-connected IPT^? ligands. The thermal stabilities and luminescence properties of 1 and 2 have also been studied. The compounds exhibit intense solid-state fluorescent emissions at room temperature.     

Construction of zinc–organic frameworks by flexible aliphatic dicarboxylates plus 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole ligand

Three new Zn(II) complexes, [Zn(ox)(imb)] (1), [Zn₂(mal)₂(imb)₂] (2), and [Zn(suc)(imb)]·H₂O (3) (imb = 2-(1H-imidazolyl-1-methyl)-1H-benzimidazole, H₂ox = oxalic acid, H₂mal = malonic acid, H₂suc = succinic acid), have been synthesized and structurally characterized. Complex 1 is a 3-D framework with a 4-connected diamond topology with the topological notation of 6⁶. Complex 2 exhibits 2-D layers with (6,3) networks. Complex 3 displays a 3-D framework constructed through unusual 2-D → 3-D parallel interpenetration of corrugated 2-D (6,3) networks. IR spectra, PXRD patterns, thermogravimetric curves, and photoluminescence spectra are addressed.     

Preparation and characterization of four polymeric metal complexes based on the flexible ligand 1H-1,2,4-triazole-1-propionic acid in different conformations

Three 2-D layered coordination polymers with (4,4) topology, {[Cu(trzp)₂(H₂O)]·1.18H₂O} _n (1), {[Co(trzp)₂(H₂O)₂]·2H₂O} _n (2), and {[Cd(trzp)₂(H₂O)]·2H₂O} _n (3), have been synthesized with the flexible, bifunctional ligand 1H-1,2,4-triazole-1-propionate (trzp^?) as a two-connected bridge. In addition, a complicated 3-D MOF [Ag₃(trzp)₂(NO₃)] _n (4) has been obtained with the help of Ag?Ag interactions and trzp^? as a four-connected linker. Htrzp and 1–4 have been characterized by single-crystal X-ray diffraction, elemental analysis, and infrared spectroscopy. The structural analysis showed that Htrzp has a gauche conformation in the solid state. However, both gauche and trans conformers of trzp^? are observed in the crystals of 1; only one conformer of trzp^? exists in the other three compounds (trans conformation in 2 and 3, and gauche conformation in 4). The thermal behaviors of 1–4 have been examined by thermal gravimetric analysis under nitrogen, which revealed that metal cyanide salts M(CN) _n (M?=?Cu(II), Co(II), Cd(II), and Ag(I), n?=?1 or 2) may be an intermediate pyrolytic decomposition product of the corresponding compounds.     

Synthesis and crystal structures of Cd(II), Ni(II), and Mn(II) complexes of 1H-benzotriazole-1-acetic acid

Three new complexes: [Cd(btaa)(bipy)(CH₃COO) · H₂O] _n (1), [Ni(btaa)₂(H₂O)₄ · 6H₂O] _n (2), and [Mn(btaa)₂(H₂O)₂] _n (3) (bipy = 2,2′-bipyridine, Hbtaa = 1H-benzotriazole-1-acetic acid) were prepared and characterized by IR, elemental analyses, thermogravimetric analyses, and single-crystal X-ray analyses. In 1, cadmium ions are linked by btaa ligands into 1-D linear chains; the chains are extended into layers through C–H ··· O hydrogen bonds and π–π stacking interactions. Complex 2 is a mononuclear structure, extended to a 3-D network through multiple intermolecular hydrogen bonds. In 3, manganese is bridged by carboxylate groups of btaa in the syn–skew bidentate mode in two directions to form a 2-D grid-like framework with a (4, 4) topology. The solid-state fluorescence spectrum of 1 shows that the excitation peak is at 355 nm while the maximum emission peak is at 424 nm.     

Syntheses,crystal structures,and catalytic activities of three new Cu(II) coordination polymers based on 2-(1H-1,2,4-triazole)-1-acetic acid

Three new coordination polymers, {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(ClO₄)} _n (1), {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(BF₄)} _n (2), and {[Cu(trza)(4,4′-bipy)]?·?(H₂O)?·?(ClO₄)} _n (3) (Htrza?=?2-(1H-1,2,4-triazole)-1-acetic acid), have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 exhibit 1-D chain structure while 3 displays 2-D layer structure. The catalytic activities of 1 and 3 in the green oxidative coupling of 2,6-dimethylphenol have been investigated.     

Self-assembly of three 1-D zinc–benzenedicarboxylate coordination polymers with 1,10-phenanthroline

Three zinc(II) benzenedicarboxylate coordination polymers, {Zn^II(L₁)(phen)(H₂O)} _n (1), {[Zn^II(L₂)(phen)]₂} _n (2), and {[Zn^II(L₃)(phen)(H₂O)]} _n (3) (L_1?=?1,4-benzenedicarboxylic dianion, L_2?=?1,3-benzenedicarboxylic dianion, L_3?=?1,2-benzenedicarboxylic dianion, and phen?=?1,10-phenanthroline), have been synthesized by self-assembly. Structural analyses of 1–3 reveal that the compounds are one-dimensional (1-D) chains. However, the structural motifs for 1–3 are distinct from each other, where 1 forms 1-D zig-zag chains, 2 is in 1-D ladder-like motif, and 3 is a 1-D helical form. Compounds 1–3 exhibit photoluminescence with emission maxima at ca 371, 392, and 375?nm, respectively.     

两个基于4-(1H-1,2,4-三氮唑)苯甲酸的稀土配位聚合物的合成、晶体结构及荧光性质(英文)

以4-(1H-1,2,4-三氮唑)苯甲酸为配体,采用水热法合成了2种稀土配位聚合物[Tb(tbc3)(H2O)3]n(1)和{[Nd(tbc3)(H2O)3]·H2O}n(2)(Htbc=4-(1H-1,2,4-三氮唑)苯甲酸)。运用X-射线单晶衍射法对该配位聚合物进行了结构测定,并对其进行了元素分析、红外光谱、TG及荧光光谱表征。单晶结构表明,配位聚合物1为三斜晶系,空间群P1,配位聚合物2属于单斜晶系,空间群为P21/c。配位聚合物1和2均为一维链结构,均通过非共价键作用形成三维超分子构造。     

Construction of three metal-organic frameworks based on multifunctional T-shaped tripodal ligands (4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide

Three metal-organic frameworks, [Eu(C₁₀H₆N₃O₅)₃(H₂O)₂]?·?H₂O (1), [Tb(C₁₀H₆N₃O₅)₃(H₂O)₂]?·?H₂O (2), and [Cd(C₁₀H₆N₃O₅)₂Cl₂] (3) based on T-shaped tripodal ligands 3-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide and 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide (H₃DCImPyO), have been synthesized by the hydrothermal method and characterized by elemental analysis, IR, and single-crystal X-ray structure analysis. The diverse coordination modes of H₃DCImPyO ligands have afforded the three compounds. Complexes 1 and 2 are isomers and the Ln (Ln?=?Eu or Tb) atoms have coordination number eight with a distorted square prism geometry. The partly deprotonated H₂DCImPyO^? ligands display three different coordination modes to link Ln (Ln?=?Tb or Eu) into 1-D double chains. In 3, Cd(II) lies on an inversion center and displays a slightly distorted octahedral coordination. All three compounds exhibit strong fluorescent emissions in the solid state at room temperature.     

Synthesis and characterization of polymeric triphenyltin and cyclotetrameric tricyclohexyltin 2-(1H-imidazol-1-yl)acetates

The reaction of 2-(1H-imidazol-1-yl)acetic acid with (Ph₃Sn)₂O or Cy₃SnOH (Cy?=?cyclohexyl) yields triphenyltin 2-(1H-imidazol-1-yl)acetate (1) and tricyclohexyltin 2-(1H-imidazol-1-yl)acetate (2), respectively. 2-(1H-imidazol-1-yl)acetates in these two complexes show remarkably different coordination modes. Complex 1 forms a polymeric chain structure through intermolecular Sn–N interactions, while 2 displays a 28-membered macrocyclic tetranuclear structure by the assembly of Sn–N coordination bonds.     

Hydrothermal synthesis,structure, and photoluminescence of four complexes based on 1H-imidazole-4,5-dicarboxylate or 1H-imidazole-2-carboxylate ligands

Four complexes, [Ag₄(bipy)₂(Himdc)₂(H₂O)₂] _n (1), [Ag(H₂imdc)] _n (2), [K(H₃imdc)(H₂imdc)(H₂O)₂] _n (3), and [Cu(Himc)₂] (4) (H₃imdc?=?1H-imidazole-4,5-dicarboxylic acid, H₂imc?=?1H-imidazole-2-carboxylic acid, and bipy?=?4,4′-bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis and elemental analysis. The obtained complexes exhibit different coordination structures; 1 contains a 2-D supramolecular layer based on two chains arraying uniformly in an ABAB manner. Compound 2 displays sawtooth-shaped 1-D chains extending to 2-D layers via hydrogen bond interactions. Compound 3 possesses a 3-D framework structure based on a 1-D chain via hydrogen bonding interactions. Compound 4 has a 3-D framework structure bearing a pcu-type topology. In addition, the photoluminescence for 1 has been investigated.     

1-D zigzag double-chain coordination polymers of transition metals derived from pyridine-2,3,5,6-tetracarboxylic acid

Three new 1-D zigzag coordination polymers {[M₂(pdtc)(bpy)₂(H₂O)₃]?·?4H₂O} _n [M?=?Zn (1), Ni (2), Co (3)] (H₄pdtc?=?pyridine-2,3,5,6-tetracarboxylic acid, bpy?=?2,2′-bipyridine) have been synthesized by the reactions of H₄pdtc and corresponding metal salts in the presence of bpy at room temperature and characterized by elemental analyses, IR, TGA, fluorescence, and X-ray diffraction. The main structural feature of 1–3 is the presence of octahedrally coordinated M1(II) and M2(II) centers sequentially bridged by pdtc ligands; bpy acts as a blocking ligand to avoid further polymerization. These coordination modes lead to 1-D double-chain structures. The 2-D or 3-D supramolecular structures of 1–3 are built up by π?···?π and hydrogen-bond interactions. Two (H₂O)₃ clusters are observed in 1–3. The zinc complex shows strong fluorescent emission at 325?nm.     

Polycondensation of Tris(Trimethylsilylseleno)Phosphane

Abstract

Tris-(trimethylsilyl)phosphane and their organo substituted derivatives (Me₃Si)_3?nP(Me₃C)_n (n: 0, 1, 2) (la-c) had been found suitable for the insertion of selenium into the phosphorus-silicon bond. At deep temperatures all silylselenophosphanes of the series (Me₃SiSe)_3?nP(Me₃C_n) (2a-c) are formed in a nearly quantitative reaction, if no excess selenium is present. (Me₃C)(Me₃SiSe)₂P=Se (3b) and (Me₃C)₂(Me₃SiSe)P=Se (3c) are detectable in small quantities as the only by-products of the reaction of (Ib-c), whereas (la) end in the formation of (2a) and traces of the dimer (Me₃SiSe)₂P-P(SeSiMe₃)₂ (4). On exposure to light or at elevated temperatures (2a) undergoes a disproportionation, forming Se=P(SeSiMe₃)₃ (3a), and the heterocycles P₃Se₄(SeSiMe₃) (5) and α-P₄Se₃(SeSiMe₃)₂ (6). (Me₃Si)₂Se is spUt off as a condensation product. After further irradiation or prolonged standing at room temperature, an insoluble oligomer is formed. The constitutions of (2-6) were determined by the analysis of their ³¹P- and ⁷⁷Se-nmr spectra.     

Half-sandwich complexes of lanthanides with tridentate ligands [RCH2CH(O)CH2OBun]2– (R = C5H4, 1-C9H6): synthesis,structures, and properties. The crystal structure of the complex {[(η5-C5H4)CH2CH(μ2:η1-O)CH2OBun]LaN(SiMe3)2}2

The oxirane-ring opening of butyl glycidyl ether with cyclopentadienylsodium or indenylsodium afforded cyclopentadienyl- and indenyl-substituted alcohols RHCH₂CH(OH)CH₂OBuⁿ (R = C₅H₄ (1) or 3-C₉H₆ (2), respectively), which were used as tridentate ligands. The reactions of these compounds with Ln[N(SiMe₃)₂]₃ produced the lanthanide complexes {[(⁵-R)CH₂CH(²:¹-O)CH₂OBuⁿ]LnN(SiMe₃)₂}₂ (R = C₅H₄, Ln = La (3), Pr (4), Er (5), Lu (6); or R = 1-C₉H₆, Ln = La (7)). The coordination spheres of the metal atoms in these complexes involve simultaneously the ⁵-cyclopentadienyl (indenyl), bridging alkoxide, and terminal amide ligands. The complexes were characterized by microanalysis, IR and NMR spectroscopy, and magnetochemistry. The crystal and molecular structure of complex 3 was established by single-crystal X-ray diffraction analysis.     

Supramolecular hydrogen bond framework constructed by 1-aminoethylidenediphosphonic acid and monovalent ions: Li + , Na + , and

Four new monovalent 1-aminoethylidenediphosphonates, [Li(AEDPH₃)(H₂O)]₆ (1), Na₂(AEDPH₃)₂(H₂O)₈ (2), (NH₄)(AEDPH₃) (3) and ((CH₃)₂NH₂)(AEDPH₃)(H₂O) (4) have been synthesized and characterized by elemental analysis, IR, TG together with X-ray single crystal diffraction analysis. Compound 1 is a 24-metallacrown-6 lithium structure, compound 2 is binuclear Na⁺ bridged by water molecules, and compounds 3 and 4 are proton-transfer salts. All four compounds are further extended to form three-dimensional (3D) supramolecular structures with the aid of water molecules (excluding 3) via various predictable hydrogen bonds.     

Syntheses and structures of three zinc coordination polymers with 1-D zigzag chain,double chain,and triple chain

Three new coordination polymers [Zn(btp)(NCS)₂] _n (1), {[Zn(btp)₂(dca)₂] _n (2), and {[Zn(btp)₃](BF₄)₂} _n (3) (btp = 1,3-bis(1,2,4-triazol-1-yl)propane, dca = dicyanamide) were synthesized and characterized. In 1, 2, and 3, one-, double-, triple-btp ligands link two Zn(II) atoms and extend to form a 1-D zigzag chain for 1, 1-D double chain for 2, and 1-D triple chain for 3. The conformations of the btp ligands in 1, 2, and 3 are analyzed. 1, 2, and 3 have emission maxima at approximately 405, 407, and 409 nm, respectively, in the solid state at room temperature.     

Synthesis,crystal structures,and fluorescence properties of transition metal complexes derived from an unsymmetrical N-heterocyclic ligand

Four transition metal complexes, [Mn(Hbimtz)₂(H₂O)₂(NCS)₂] (1), [Co(Hbimtz)₂(H₂O)₂(NCS)₂] (2), [Pb(Hbimtz)Br₂] _n (3), and {[Ag₂(Hbimtz)₃]SO₄?·?4H₂O} _n (4) (Hbimtz?=?1-[(1H-benzimidazol-2-yl)-methyl]-1,2,3,4-tetrazole), were synthesized and characterized by single-crystal X-ray diffraction. The Mn(II) of 1 and Co(II) of 2 are six-coordinate with two nitrogen atoms from Hbimtz, two nitrogen atoms from thiocyanate and two water molecules. The geometry of Pb(II) in 3 is a distorted octahedron with two nitrogen atoms of two Hbimtz's and four Br^? ions, including the weak bond between the Pb1 and N6 of Hbimtz. Complex 3 is assembled into a 1-D [PbBr₂] _n inorganic chain by μ ₂-Br^? and into a 2-D layer by weak interactions. The Ag(II) of 4 has two geometries, linear and tetrahedral. Hbimtz bridges the two kinds of Ag(II) into a 1-D helical chain. Fluorescence of 3 and 4 were also investigated.     

Temperature- and pressure-dependent utilising dimensionality cross-over of Silver(I) complex supported by short Ag···Ag Interactions

Two Ag(I)-based complexes, a mononuclear [Ag(PPh₃)₂(2tpCOO)]·EtOH (1) and a tetranuclear [Ag₄(PPh₃)₄(2tpCOO)₄] (2) have been prepared by a small tuning on the molar ratio of the reactants as well as the crystallisation method. A 1-D polymeric structure, [Ag₂(PPh₃)(2tpCOO)₂]_n (3) was obtained while the crystals of 2 were left under high temperature and autogenous pressure. The study suggests that the formation of 1-D polymeric structure is due to the removal along with the intramolecular and intermolecular reorganisation of the coordinated ligands that leads to dimensionality cross-over from 0-D to 1-D. The rearrangement of the ligands in 3 also resulted the metal centres moving closer together, being separated by 2.9626(3) Å in 3, compared to 3.215(8) Å in 2. The photoluminescence properties have been investigated showing that only complexes 2 and 3 exhibit this property at room temperature in solid state that is due to metal-to-ligand charge transfer.     

Syntheses,crystal structures,and fluorescent properties of two 2-D Cd(II) complexes based on 2-((1H-1,2,4-triazol-1-yl)methyl)-1H-benzimidazole and 1,2,4,5-benzenetetracarboxylate

Two complexes formulated as {[Cd(btec)_0.5(tmb)H₂O]·4H₂O}_n (1) and {[Cd(H₂btec)(tmb)(H₂O)]·2H₂O}_n (2) (H₄btec?=?1,2,4,5-benzenetetracarboxylic acid, tmb?=?2-((1H-1,2,4-triazol-1-yl)methyl)-1H-benzimidazole) have been synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Single crystal X-ray diffraction shows that 1 has a 2-D layer structure in which tmb bridges and all of the carboxylates from 1,2,4,5-benzenetetracarboxylate chelate. In 2 Cd(II) ions are bridged by monodentate carboxylates leading to a 2-D layer structure with all tmb ligands coordinated monodentate to Cd(II), hanging at two sides of the layers. Complexes 1 and 2 are further extended to 3-D supramolecular structures by hydrogen bonding interactions. Luminescent properties have been investigated in the solid state at room temperature.