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Treatment of [Ru 3 (CO) 12 ] with 2,5-di(2-pyridyl)pyrrole (HL1) and 2,5-di(2-(5-bromopyridyl)pyrrole (HL2) in refluxing toluene afforded the dinuclear Ru(I) carbonyl complexes [Ru 2 (CO) 4 (L)] (L = L1 ( 1 ), L2 ( 3 ), respectively). Alternatively, 1 along with a minor mononuclear product [Ru(CO) 2 (L1) 2 ] ( 2 ) was synthesized from reaction of [Ru(CO) 2 Cl 2 ] n with HL1 in methanol in the presence of triethylamine. Complexes 1 – 3 have been fully characterized by NMR, IR, UV–vis, ESI-MS, and elementary analysis. Single-crystal X-ray diffraction indicates that both 1 and 3 feature a Ru–Ru single bond and the di(pyridyl)pyrrolide ligands bind to the two Ru(I) centers in a μ-κ 2 N,N’ :κ 1 N” chelating-bridging mode. Complex 2 is mononuclear Ru(II) complex with two κ 2 N , N ’ di(pyridyl)pyrrolide ligand. The spectroscopic and electrochemical properties of 1 and 3 were also explored.

The treatment of 2-(5-(pyridin-2-yl)-1H-pyrrol-2-yl)pyridine (HL1) and PhICl2 as halogenation reagent generated monochloro-pyrrole HL2, dichloro-pyrrole HL3 and penta-chloro L4. The reaction of HL3 with [Ru(CO)2Cl2]n gave diruthenium(I) complex [Ru2(μ-κ2N,N′:κ1N″-L3)2(CO)4] (1) and monoruthenium(II) complex [Ru(κ3N,N′,N‴-L3)(κ2N,N′-L3)(CO)] (2). All these newly synthesized compounds were fully characterized by 1H NMR, IR, UV–Vis spectra, elemental analyses and X-ray diffraction study. The structural analysis shows that dichloro-pyrrole L3− acts as chelating and bridging ligand to coordinate two ruthenium atoms in 1, and acts as bidentated and tridentated ligand in 2.

The diethylphosphonate ligand HL 1 substituted pyridylpyrrole was synthesized by treatment of 2-bromo-6-(1H'-pyrrol-2-yl)pyridine and diethylphosphite in presence of base triethylamine and catalyst Pd(PPh 3 ) 4 under refluxing toluene conditions. The HL 1 ligand was treated with bromotrimethylsilane and followed hydrolysis by methanol to afford diphosphonic acid ligand H 3 L 2 . Treatment of H 3 L 2 with [Ru(NO)Cl 3 ] in presence of triethylamine in refluxing thf was generated diruthenium nitrosyl complex [Ru(L 2 )(NO)(Cl)] 2 ·(Et 3 NH) 2 ([ 1 ]·(Et 3 NH) 2 ), which is water soluble. The ligands and metal complex were fully characterized by NMR, IR, ESI-MS and single crystal X-ray diffraction technology. The solid state structure analysis displays 1 2- is dinuclear species, of which two ruthenium atoms are linked by two PO 3 2- groups. Photorelease of nitric oxide from 1 2- was monitored by UV-Vis spectra and the amount of the NO was determined by Griess reaction and DPPH radical scavenging reaction.

N,N′-diisobutyloxycarbonyl-N″,N‴-(1,3-propylene)-bisthiourea ( L ) and its silver(I) and gold(I) complexes were designed and synthesized. Treatment of 1,3-propanediamine with the isothiocyanate i PrCH 2 OC(O)NCS yielded bisthiourea L with over 90% yield. Treatment of L with AgNO 3 in CH 3 CN afforded coordination polymer {[Ag( L )(NO 3 )·CH 3 CN]} n ( 1 ) with layer structure, while with HAuCl 4 in CH 3 CN resulted in reduction of Au 3+ to Au + to yield molecular [Au( L )Cl] ( 2 ). Ligand L and complexes 1 and 2 were fully characterized by IR, 1 H NMR, UV–Vis, cyclic voltammetry and element analysis. The X-ray diffraction analysis displays that the bisthiourea L behaves as sulfur donor to coordinate to Ag and Au atom with μ 3- (S, μ 2 -S′,S′) and μ 2 -S, S′ coordination mode in 1 and 2 , respectively.

Nitrogen donor ligands HL1, HL3, HL4 and their silver complexes 1·OTf–4·OTf are prepared and fully characterized. Treatment of HL1-HL4 with AgOTf (OTf− = triflato) in presence of base Et3N and co-ligand PPh3 affords dinuclear Ag(I) complexes [Ag2(L)(PPh3)2]·OTf (L = L1−, 1·OTf; L = L2−, 2·OTf; L = L3−, 3·OTf; L = L4−, 4·OTf), respectively. The solid structure displays L acts as bis(bidentate) ligand, bridging between two Ag(I) centres. The Ag⋯Ag interaction as well as other weak interactions, such as Ag⋯Brintermolecular for 1+, Ag⋯Brintramolecular for 2+, Ag⋯S for 3+ are observed. These complexes are applied in the A3-coupling reaction of aldehydes, alkynes and amines under mild conditions, and showed excellent catalytic efficiency and recyclability. 1 mol% catalyst loading gives 99% yield of propargylamines product in 0.15 h at 35 °C in open air atmosphere. 1·OTf can be recycled six times without noticeable less of the catalyst activity.

Treatment of [Ir(PPh3)3Cl] with the 2-(1H-pyrrol-2-yl)pyridine (Hpp) ligand under refluxing toluene affords the iridium(III) hydride complex [Ir(H)Cl(pp)(PPh3)2] (1), whereas in the simultaneous presence of KOtBu the reaction gives iridium(III) hydride isomers, namely ortho-metallated triphenylphosphine cis-(P,P)-[Ir(H)(pp)(PPh3){K2C,P-PPh2(C6H4)}] (2) and trans-(P,P)-[Ir(H)(pp)(PPh3){K2C,P-PPh2(C6H4)}] (3). Complexes 1–3 are fully characterized by 1H NMR, 31P NMR, IR and UV–vis spectroscopy, together with single crystal X-ray diffraction analysis.

Five mononuclear copper(I) complexes and one dinuclear silver(I) phosphine complex containing the bispyridylpyrrole ligand were synthesized and structurally characterized. Treatment of CuCl and the deprotonated bispyridylpyrrole ligand with bis(phosphine) ligands afforded the copper(I) complexes [(PDPH)Cu(XANTPhos)] (1), [(PDPH)Cu(DPEPhos)] (2), [(PDPBr)Cu(XANTPhos)] (3) and [(PDPBr)Cu(DPEPhos)] (4), while addition of two equivalences of PPh3 gave [(PDPBr)Cu(PPh3)2] (5), where PDPH− = 2,5-bis(2-pyridyl)pyrrole, PDPBr− = 2,5-bis(6′-bromo-2′-pyridyl)-pyrrole, XANTPhos = 9,9-di-methyl-4,5-bis(diphenylphosphino)xanthene, DPEPhos = oxydi-2,1-phenylene)bis-diphenylphosphine. Reaction of PDPBr− with AgOTf and DPEPhos yielded the dinuclear silver(I) complex [(PDPBr)Ag2(DPEPhos)](OTf) (6). All of these complexes were fully characterized on the basis of IR spectra, 1H and 31P NMR spectra, elements analysis, UV–Vis spectra and X-ray single crystal diffraction analysis. The photophysical properties of these complexes were also studied.

A new class of neutral dicopper(I)–halide complexes with {Cu2(μ-X)} (X = Cl, Br and I) core supported by bispyridylpyrrole ligand have been synthesized and characterized. Replacements of chloride ligand in [Cu2(μ-X)2(PPh3)3] (X = Cl, Br, I) by the anionic PDPH− (PDPH− = 2,5-bis(2′-pyridyl)pyrrole) or PDPBr− (PDPBr− = 2,5-bis(6′-bromo-2′-pyridyl)-pyrrole) ligand gives complexes 1–6. They are [(PDPH)Cu2(μ-X)(PPh3)2] (X = Cl (1); Br (2); I (3)) and [(PDPBr)Cu2(μ-X)(PPh3)2] (X = Cl (4); Br (5); I (6)). The X-ray crystallographic studies reveal these complexes are isostructural. Two phosphine–copper(I) units are linked by one halogen atom and one nitrogen atom from bridging bispyridylpyrrole ligand to form 4-membered Cu2XN core. Each copper atom is located in the center of distorted tetrahedral geometry. The PDPH− and PDPBr− ligands display μ2-κ2(N,N′), κ2(N′,N″) bonding mode. The separation of Cu⋯Cu in 1–6 is in the range of 2.6708(15)–2.7959(6) A. The photophysical properties of 1–6 are described.

Heteropolymetallic complexes [(salen)Ti(ReO 4 ) 2 ] ( 1 ) and [{(salen)Ti(ReO 4 )} 2 (μ-O)] ( 2 ) are easily obtained in high yields via reaction of [(salen)TiCl 2 ] and [{(salen)TiCl 2 } 2 (μ-O)] with (Me 3 SiO)ReO 3 , respectively (where, salen = (S,S)- N , N ′-bis(3,5-di- tert -butylsalicylidene)cyclohexane-1,2-diamine dianion). The structure of complex 2 was established by single-crystal X-ray diffraction. The tetrahedral geometry of the ReO 4 − anion links the dititanium unit of {(salen)Ti} 2 (μ-O) in the axial positions. The Re–O–Ti bridge angles range from 146.1(2) to 162.6(2) with a Re⋯Ti separation of 3.780 A. Complexes 1 and 2 are capable of catalytic oxidation of sulfides with t BuOOH.

Ruthenium(VI) complexes with a sterically bulky bidentate Schiff base ligand, 2-[(2,6-diisopropylphenyl)imino]methyl-4,6-dibromophenolate (L−), have been synthesized and their reactivity studied. Treatment of [Bun4N][Ru(N)Cl4] in tetrahydrofuran with 2 equivalents of NaL afforded cis-[Ru(N)Cl(L)2] (1) that reacted with Ag(OTf) (OTf− = triflate) in acetone to give trans-[Ru(N)(H2O)L2][OTf] (2). Reactions of complex 1 with Me3NO and elemental sulfur afforded cis-[Ru(NO)(Cl)L2] (3) and cis-[Ru(NS)(Cl)L2] (4), respectively. Reaction of complex 1 with Me3SiN3 in MeCN afforded [Ru(MeCN)(Cl)L2], which could alternatively be prepared by photolysis of complex 3 in CH2Cl2–MeCN with UV light. The crystal structures of complexes 1 and 2 have been determined.

Treatment of [Ru( CHR)Cl2(PCy3)2] (Cy = cyclohexyl) with Tl[N(Pr2iPO)2] and AgLOEt (LOEt− = [CpCo{P(O)(OEt)2}3]−) afforded the Ru carbene complexes [Ru( CHPh)(PCy3)Cl{N(Pr2iPO)2}] (1) and [LOEtRu( CHR)(PCy3)Cl] (2), respectively. Chloride abstraction of complex 2 with TlPF6 in MeCN afforded [LOEtRu( CHPh)(PCy3)(MeCN)][PF6] (3). Complexes 1 and 2 are capable of catalyzing ring-closing metathesis of diethyl 1,2-diallylmalonate. The crystal structure of complex 2 has been determined.

A novel compound Cu(phen)(m-CBA) 2 was synthesized with m-chlorobenzoic acid(m-CBA), 1,10-phenanthroline(phen) and Cu(OAc) 2 ·H 2 O. It was characterized by IR, UV, elemental analyses and X-ray crystallography. It crystallizes in the monoclinic crystal system with C 2/ c space group, a =2.9699(4) nm, b =1.15452(2) nm, c =1.5335(2) nm, β=111.118(2)°, V =4.905 1(1) nm 3 , Z =8, F (000)=2 328, R 1 =0.072 8, w R 2 =0.223 4 [ I >2σ( I )]. Structure analysis shows that the copper center coordinates with two nitrogen atoms from one 1,10-phenanthroline molecule, two oxygen atoms from two m-chlorobenzoic acid molecules, giving a distorted squared planar coordination geometry. This novel compound shows paramagnetic interactions between copper centers.

The interaction of [Et4N]2[Cd4(SPh)10] with CuI in DMF–MeCN in the presence of PPh3 gave the metal cluster ion-pair [Cu8(μ4-SPh)6(PPh3)4(MeCN)4][Cu(μ-SPh)6(CdI)3] (1), with a cationic octanuclear copper(I) cage cluster and an anionic mixed-metal complex. Reaction of CuI and NaSPh in DMF in the presence of PPh3 resulted in the formation of a neutral octanuclear copper(I) cluster [Cu8(μ-SPh)4(μ3-SPh)4(PPh3)4] (2), whereas the similar reaction of CuI and NaSPh-4-Me led to the isolation of a neutral tetradecanuclear copper(I) cluster [Cu14(μ6-S)(μ-SPh-4-Me)12(PPh3)6] (3). Similarly, treatment of AgBr with NaSPh in DMF in the presence of PPh3 afforded a cationic bromide-centered tetradecanuclear silver(I) cage cluster [Ag14(μ6-Br)(μ3-SPh)12(PPh3)8]Cl (4). The structures of the clusters 1–4 were determined by single-crystal X-ray diffraction analyses.

Two new 2D 3d-4f heterometallic compounds [LnIIICuII(2,4′-bpdc)2(μ3-OH)(C2H5OH)H2O]n (Ln = Tb(1) and Eu(2), 2,4′-H2bpdc = 2,4′-biphenyldicarboxylic acid) have been successfully constructed by the solvothermal reaction of Ln2O3, Cu(NO3)2 and 2,4′-H2bpdc in ethanol, and characterized by element analysis, IR spectroscopy, and thermal analysis, as well as single crystal X-ray diffraction. The results reveal that two complexes are isomorphous and exhibit 2D pillar-chained coordination frameworks with 36·46·53 topology constructed from one-dimensional lanthanide-transition oxo-bridged heterometallic chains [LnCu(μ2-O)2(μ3-OH)2]n and (2,4′-bpdc2−)2 pillars. Furthermore, the photoluminescent properties of two compounds 1 and 2 were also studied.

A new 2D samarium compound [Sm(2,4′-bpdc)(2,4′-Hbpdc)H2O]n (1) (2,4′-H2bpdc = 2,4′-biphenyldicarboxylic acid) has been successfully constructed by the hydrothermal reaction of Sm2O3 with 2,4′-H2bpdc, and characterized by elemental analysis, IR spectroscopy and thermogravimetric analysis, as well as single-crystal X-ray diffraction. The results reveal that complex 1 possesses a 2D framework with 44 topology constructed from one-dimensional lanthanide-carboxylate meso-helical chains [Sm(O–C–O)2]n (Δ + Λ) and (2,4′-bpdc2−)2 pillars; this complex represents the first example of a lanthanide compound containing 2,4′-biphenyldicarboxylate as the sole ligand. Moreover, compound 1 displays a certain photoluminescent property and high thermal stability.

A new 2D cadmium compound [Cd(2,4′-bpdc)H2O]n ( 1 ) (2,4′-H2bpdc = 2,4′-biphenyldicarboxylic acid) has been successfully synthesized by the hydrothermal reaction of Cd(Ac)2 and 2,4′-H2bpdc, and characterized by element analysis, IR spectroscopy and thermal analysis, as well as single-crystal X-ray diffraction. The results reveal that complex 1 possesses a 2D framework with one-dimensional nano-channels hinged by two meso-helical chains sharing two Cd centers through 2,4′-bpdc2− ligands, which denotes the first example of the complex including single 2,4′-biphenyldicarboxylate ligand. Moreover, compound 1 displays a strong photoluminescent property and high thermal stability.

A new pillar-layered coordination framework [Er(H2O)(C5H2N2O4)(TA)0.5]n (1) has been hydrothermally synthesized by employing imidazole-4,5-dicarboxlylate (H3IDC) and terephthalate (H2TA) and structurally characterized. Single crystal X-ray diffraction analysis reveals that compound 1 exhibits the 2D pillar-layered coordination framework with meso-helical character constructed from auxiliary ligand TA2− (that is, pillar) bridging two [Er(HIDC2−)]n layers (namely, Δ- and Λ-layers), which is the first example of lanthanide coordination framework including imidazole-4,5-dicarboxlylate and terephthalate. Meanwhile, the thermogravimetric analysis shows compound 1 has high thermal stability.

Treatment of [Cp∗Ir(ppy)Cl] (Cp∗ = η5-C5Me5, ppyH = 2-(2-pyridyl)phenyl) with Ag(OTf) (OTf− = triflate) in MeOH and MeCN gave the solvento complexes [Cp∗Ir(ppy)(solv)][OTf] (solv = MeOH (1) and MeCN (2)). Complex 1 is capable of catalyzing oxidation and azirdination of styrene with PhIO and PhINTs (Ts = tosyl), respectively. Treatment of 2 with a stoichiometric amount of PhINTs resulted in the insertion of the NTs group into the Ir–C(ppy) bond and formation of [Cp∗Ir(η2-ppy-NTs)(MeCN)][OTf] (3). Treatment of 1 with R2E2 afforded [Cp∗Ir(ppy)(η1-R2E2)][OTf] (E = S (4), Se (5), Te (6)). Reactions of 4 and 5 with Ag(OTf) resulted in cleavage of the E–E bond and insertion of an ER group into the Ir–C(ppy) bond. The crystal structures of complexes 2–6 and [Cp∗Ir(η2-ppy-S-p-tol)(H2O)][OTf]2 have been determined.

Treatment of [Bun4N][Ru(N)Cl4] with Na(OR) afforded [Bun4N][Ru(N)(OR)4] (R = C6F5 (1), C6F4H (2), C6Br5 (3)), whereas that with [Bun4N][Os(N)Cl4] gave [Bun4N][Os(N)(OR)3Cl] (R = C6F5 (4), C6F4H (5), C6Br5 (6)). Treatment of [Bun4N][M(N)Cl4] with Na(SC6F4H) and Na(Sxyl) (xyl = 2,6-dimethylphenyl) afforded [Bun4N][M(N)(SC6F4H)4] (M = Ru (7), Os (8)) and [Bun4N][M(N)(Sxyl)4] (M = Ru (9), Os (10)), respectively. The crystal structures of compounds 1, 6 and 9 have been determined.

Interaction of [LOEtZrF3] ( L OEt - = [Co(η5-C5H5){P(O)(OEt)2}3]−) (1) with 3 equivalents of bis(trimethylsilyl) sulfate afforded the ZrIV hydrogensulfato complex [(LOEt)2Zr2(SO4)2(HSO4)2] (2) that reacted with Et3N to give [Et3NH][LOEtZr(H2O)(SO4)2] (3). Treatment of complex 1 with 3 equivalents of trimethylsilyl acetate afforded [LOEtZr(OCOCH3)3] (4), whereas that with 1 and 2 equivalents of trimethylsilyl trimethylsiloxyacetate yielded [LOEtZrF(OCOCH2O)]2 (5) and [LOEtZr(OCOCH2OH)(OCOCH2O)]2 (6), respectively. The crystal structures of complexes 2 and 6 have been determined.

The Klaui oxygen tripodal ligands [(η 5 -C 5 H 5 )Co{P(O)(OR) 2 } 3 ] − (L OR − where R = alkyl group), which have been recognized as oxygen analogues of cyclopentadienyl, can form stable complexes with a range of main group and transition metal ions. This review reports on the recent developments in the coordination and organometallic chemistry of the Klaui tripodal ligands. Special attention will be paid to polynuclear M-L OEt (M = Ti, Zr) oxo and hydroxo compounds that may serve as models for group 4 metal aqua ions.

Treatment of [Ti(OPri)2Cl2] with K(tpip) (tpip− = [N(PPh2O)2]−) followed by chlorination with HCl afforded cis-[Ti(tpip)2Cl]2 (1). Reduction of 1 with Na/Hg in THF gave [Ti(tpip)3] (2), which could also be prepared from [TiCl3(THF)3] and K(tpip). Recrystallization of [V(O)(tpip)2] (3) from CH2Cl2–Et2O in air afforded trinuclear [{V(O)}3(μ-tpip)3(μ-O)3] (4). Treatment of [Cr(NBut)2Cl2] and [Cr(NBut)Cl3(dme)] (dme = 1,2-dimethoxyethane) with [Ag(tpip)]4 led to isolation of [Cr(tpip)3] (6) and [Cr(NBut)(tpip)2Cl] (7), respectively. The Ti- and V-tpip complexes are capable of catalyzing oxidation of sulfides with tert-butyl hydroperoxide and H2O2. The crystal structures of 1, 2, and 4 have been determined.

Treatment of [L OEt Ti(OTf) 3 ] ( L OEt − = [ CpCo { P ( O ) ( OEt ) 2 } 3 ] - , OTf − = triflate) with S -binapO 2 (binap = 2,2′-bis(diphenylphosphinoyl)-1,1′-binaphthyl) afforded the terminal hydroxo complex [L OEt Ti( S -binapO 2 )(OH)][OTf] 2 ( 1 ). Treatment of [L OEt Ti(OTf) 3 ] with K(tpip) (tpip − = [N(Ph 2 PO) 2 ] − ) afforded [L OEt Ti(tpip)(OTf)][OTf] ( 2 ) that reacted with CsOH to give [L OEt Ti(tpip)(OH)][OTf] ( 3 ). The structures of 1 and 2 have been determined.

This paper describes the hydrothermal syntheses and characterization of two antimony(III) diphosphonates: [NH3(CH2)nNH3]Sb{CH3C(O)(PO3)2} [n=4 (1), 5 (2)]. The two compounds are isostructural based on their XRD measurements. Single-crystal structure determination of compound 1 revealed a one-dimensional linear chain structure where the distorted {SbO5E} octahedra (E is the lone pair electrons occupying an axial position) are corner-shared by {CPO3} tetrahedra. The protonated diamines are located between the chains, with their nitrogen atoms locked by the hydrogen bonds with the phosphonate oxygens. Crystal data for 1: orthorhombic, space group Pnma, a=13.426(4), b=17.149(4), c5.4496(14) A, V=1254.7(6) AA3, Z=4.