Mono- and heterodimetallic FeII and RuII complexes based on a novel heteroditopic 4′-{bis(phosphanyl)aryl}-2,2′:6′,2″-terpyridine ligand

In the search for a versatile building block that allows the preparation of heteroditopic tpy-pincer bridging ligands, the synthon 14'-[C6H3(CH2Br)(2)-3,5]-2,2':6',2 ''-terpyridine was synthesized. Facile introduction of diphenylphosphanyl groups in this synthon gave the ligand 14'-[C6H3(CH2PPh2)2-3,5]-2,2':6',2"-terpyridine) ([tpyPC(H)Pj). The asymmetric mononuclear complex [Fe(tpy){tpyPC(H)P}](PF6)(2), prepared by selective coordination of [Fe(tpy)Cl-3] to the tpy moiety of [tpyPC(H)P], was used for the synthesis of the heterodimetallic complex [Fe(tpy)(tpyPCP)Ru(tpy)](PFC,)3, which applies the "complex as ligand" approach. Coordination of the ruthenium centre at the PC(H)P-pincer moiety of [Fe(tpy){tpyPC(H)P}](PF6)(2) has been achieved by applying a transcyclometallation procedure. The ground-state electronic properties of both complexes, investigated by cyclic and square-wave voltammetries and UV/Vis spectroscopy, are discussed and compared with those of [Fe(tPY)(2)](PF6)(2) and [Ru(PCP)(tpy)]Cl, which represent the mononuclear components of the heterodinuclear species. An in situ UV/Vis spectroelectrochemical study was performed in order to localize the oxidation and reduction steps and to gain information about the Fe-II-Ru-II communication in the heterodimetallic system [Fe(tpy)(tpyPCP)Ru(tpy)](PF6)(3) mediated by the bridging ligand [tpyPCP]. Both the voltammetric and spectroelectrochemical results point to only very limited electronic interaction between the metal centres in the ground state.

A square-planar nickel(II) monoradical complex with a bis(salicylidene)diamine ligand

The new square-planar Ni-II-N2O2 complex [Ni(L-Me)] (1(Me)), where L-Me, stands for the dianionic phenolato form of N,N'bis(3,5-di-tert-butyl-salicylidene)-4,5-dimethyl-1,2-phenyl- enediamine ((LH2)-L-Me), has been synthesised and fully characterised. X-ray crystallography was also used for the characterisation. The electrochemical one-electron oxidation of 1(Me) produces the thermally stable (within the temperature range 10-295 K) cationic species (1(Me))(+). The UV/Vis and X-band EPR experimental data, supported by DFT calculations, indicate that (1(Me))(+), is best described as a Ni-II monoradical complex and, thus, does NOT exist in a Ni-III ground state, in contrast to its demethylated counterpart [Ni(L-H)](+) (1(H))(+) below 170 K.

Diorganoruthenium complexes incorporating noninnocent [C6H2(CH2ER2)2-3,5]22-(E = N, P) Bis-Pincer bridging ligands: synthesis, spectroelectrochemistry, and DFT studies

The dinuclear complex [(tpy)Ru-II(PCP-PCP)Ru-II(tPY)]Cl-2 (bridging PCP-PCP = 3,3',5,5'-tetrakis(diphenylphosphinomethyl)biphenyl, [C6H2(CH2PPh2)(2)-3,5](2)(2-)) was prepared via a transcyclometalation reaction of the bis-pincer ligand [PC(H)P-PC(H)P] and the Ru(II) precursor [Ru(NCN)(tpy)]Cl (NCN = [C6H3(CH2NMe2)(2)-2,6](-)) followed by a reaction with 2,2':6',2 ''-terpyridine (tpy). Electrochemical and spectroscopic properties of [(tpy)Ru-II(PCP-PCP)Ru-II(tPY)]Cl-2 are compared with those of the closely related [(tpy)Ru-II(NCN-NCN)Ru-II(tpy)](PF6)(2) (NCN-NCN = [C6H2(CH2- NMe2)(2)-3,5](2)(2-)) obtained by two-electron reduction of [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](PF6)(4). The molecular structure of the latter complex has been determined by single-crystal X-ray structure determination. One-electron reduction of [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](PF6)(4) and one-electron oxidation of [(tpy)Ru-II(PCP-PCP)RUII(tpy)]Cl-2 yielded the mixed-valence species [(tpy)Ru-III(NCN-NCN)RUII(tpy)](3+) and [(tpy)Ru-III(PCP-PCP)RUII(tpy)](3+), respectively. The comproportionation equilibrium constants K-c (900 and 748 for [(tpy)Ru-III(NCN-NCN)Ru-III(tpy)](4+) and [(tpy)Ru-II(PCP-PCP)RUII(tpy)](2+), respectively) determined from cyclic voltammetric data reveal comparable stability of the [Ru-III-Ru-II] state of both complexes. Spectroelectrochemical measurements and near-infrared (NIR) spectroscopy were employed to further characterize the different redox states with special focus on the mixed-valence species and their NIR bands. Analysis of these bands in the framework of Hush theory indicates that the mixed-valence complexes [(tpy)Ru-III(PCP-PCP)RUII(tpy)](3+) and [(tpy)Ru-III(NCN-NCN)RUII(tpy)](3+) belong to strongly coupled borderline Class II/Class III and intrinsically coupled Class III systems, respectively. Preliminary DFT calculations suggest that extensive delocalization of the spin density over the metal centers and the bridging ligand exists. TD-DFT calculations then suggested a substantial MLCT character of the NIR electronic transitions. The results obtained in this study point to a decreased metal-metal electronic interaction accommodated by the double-cyclometalated bis-pincer bridge when strong sigma-donor NMe2 groups are replaced by weak sigma-donor, pi-acceptor PPh2 groups

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.

Synthesis and structural studies of a bis(carbamoyl methyl) sulfoxide complex of uranyl nitrate

A new tri-functional ligand iBu2NCOCH2SOCH2CONiBu2 was prepared and characterized. The coordination chemistry of this ligand with uranyl nitrate was studied with IR, 1H NMR, electrospray mass-spectrometry, thermogravimetry, and elemental analysis. The structure of [UO2(NO3)2(iBu2NCOCH2SOCH2CONiBu2)] was determined by single-crystal X-ray diffraction. The uranium(VI) ion is surrounded by eight oxygens in a hexagonal bipyramidal geometry. Four oxygens from two nitrates and two oxygens from the ligand form a planar hexagon. The ligand is a bidentate chelate, bonding through sulfoxo and one of the carbamoyl groups to uranyl nitrate.

Room temperature synthesis of tri-, tetrasubstituted imidazoles and bis-analogues by mercaptopropylsilica (MPS) in aqueous methanol: application to the synthesis of the drug trifenagrel

The heterogeneous solid catalyst, mercaptopropylsilica (MPS), has been prepared by a modified procedure in water and its structure confirmed by solid state carbon-13 CP-MAS NMR spectrum. This catalyst has been efficiently utilized for the synthesis of a wide variety of tri-, tetrasubstituted imidazoles and their bis-analogues at room temperature. The protocol was further explored for the synthesis of the drug trifenagrel.

Synthesis, characterization and molecular structure of 1,1′ bis(diphenylphosphino ferrocene)dioxide complex of uranyl nitrate

A 1,1' bis(diphenylphosphino ferrocene) dioxide complex of uranyl nitrate was synthesized and characterized by IR, H-1 and P-31{H-1} NMR spectroscopic and X-ray diffraction methods. The structure of the compound shows that the uranium atom is surrounded by eight oxygen atoms in a hexagonal bi-pyramidal geometry. Two oxygen atoms from 1,1' bis(diphenylphosphino ferrocene) dioxide ligand and four oxygen atoms from the nitrate groups form a planar hexagon. The two uranyl oxygen atoms occupy the axial position. The 1,1' bis(diphenylphosphino ferrocene) dioxide ligand acts as a bidentate chelating ligand with a bite angle of 71.56(8)degrees around the uranium(VI) atom, which is much smaller in value compare to any of the previously reported values (90.1 degrees-154.0 degrees) for this ligand.

Highly efficient separation of actinides from lanthanides by a phenanthroline-derived bis-triazine ligand

The synthesis, lanthanide complexation, and solvent ex- traction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-triazine ligand are described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis-complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respec-tively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligand's properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone.

Configurational preferences of two 1,2-diamine adducts of bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)

The preparation, the IR and ligand field spectra and the structures of the mixed-ligand addition compounds [(N,N-dimethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me2en], and [(N,N,N′,N′-tetramethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me4en], are reported. The structures were determined by single crystal X-ray diffraction analysis (monoclinic, space group P21/c, Z=4 with a=10.708(6), b=19.531(6), c=13.352(6) Å, β=111.64(10)°, R1=0.0642 and wR2=0.1719 for [Co(thtf)2(me2en)] and a=12.033(6), b=15.565(6), c=15.339(6) Å, β=92.57(6)°, R1=0.0612 and wR2=0.1504 for [Co(thtf)2me4en]). The structures are distorted octahedral and the shortest cobalt–cobalt separation distances are 5.388(2) Å in [Co(thtf)2me2en] and 8.675(3) Å in [Co(thtf)2me4en]. In both compounds the diamine molecules attain the gauche conformation. The U(Z,Z) conformation of the β-dione leads to a semi-chair conformation of the β-dionato chelate rings. The relative orientation of the groups attached to the β-dionato moiety depends on the extent of stereoelectronic effects the N-substitution of the diamine entails. In [Co(thtf)2me2en] the intraligand distance separating the trifluoromethyl carbon atoms is 5.281(18) Å while in [Co(thtf)2me2en] it increases to 8.338(9) Å. The cobalt–cobalt separation distance, the orientation of the chelate rings and the extent of N-substitution seem to affect hydrogen bonding. While in [Co(thtf)2me2en] inter- and intraligand hydrogen bonding is implicated, it is totally absent in [Co(thtf)2me4en].

A simplified, high-yield synthesis, and crystal structure of [tris{bis(2,4,6-triisopropylphenyl)tin}]

The species [{Sn(C2H2iPr3-2,4,6)2}3] has been obtained in a simple, essentially quantitative, synthesis from SnCl2 and ArLi in diethyl ether at low temperature. The crystal structure analysis confirms the trimeric nature of the molecular units but reveals some unusual features. The crystal contains the unusual feature of an asymmetric unit that consists of three units of [{SnAr2}3] in P21/c; the molecular unit is a scalene triangle, showing high consistency between the three molecules, in contrast to analogous trimeric species of silicon or germanium. The SnSn bonds are lengthened (average value 2.942 Å) owing to steric crowding.

Reaction of 1,1′-diacetylferrocene with hydrazine hydrate: Synthesis and X-ray crystal structures of bis(hydrazine)bis(hydrazinecarboxylato-N′,O)iron(II), [Fe(N2H4)2(O2CNHNH2)2], and the cyclic biferrocene diazine, [N(Me)CC5H4FeC5H4C(Me)N]2

1,1′-Diacetylferrocene reacts with neat hydrate over a period of 72 h at 20°C to give the dihydrazone [H2NN(Me)CC5H4FeC5H4C(Me)NNH2] (6) in almost quantitative yield. Either prolonging the reaction time or reacting 6 with fresh hydrazine causes the iron to be stripped from the metallocene and bis(hydrazine)bis(hydrazinecarboxylato-N′,O) iron(II), [Fe(N2H4)2(OOCNHNH2)2] (11), crystallizes. In the presence of Ba2+ or Mo2+ ions two molecules of complex 6 react to give the cyclic diazine [N(Me)CC5H4FeC5H4C (Me)N]2 (7) in high yield. Hydrazine is liberated in this reaction. Complexes 6 and 11 have been characterized crystallographically. The cyclic voltammograms of complexes 6 and 7 contain essentially non-reversible oxidation peaks.

μ-Peroxo-μ-oxo-bis[bis(trimethylsilylmethyl)tin]: the first structurally characterised main-group metal η2-peroxide, a formal tin analogue of an ozonide

The title compound is the first µ-η2-peroxodimetallic species to be characterised for a main group metal, possessing a long peroxo O–O bond, and large C–Sn–C angles, and is an unexpected product from the oxidation of [SnR2][R = CH(SiMe3)2], with a structure analogous to an organic ozonide.

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Isolation, structure, chemistry, and photochemistry of cis-bis(2,2'-bipyridyl)carbonylchlororuthenium(II) perchlorate

The molecular structure and chemical and photochemical reactions of [Ru(bpy)2(CO)Cl]+ClO4–, which has been isolated from the reaction of ruthenium trichloride and 2,2′-bipyridyl(bpy) in dimethylformamide, are described.