Anchoring selenido-carbonyl ruthenium clusters to functionalised silica xerogels

Silica Xerogels containing carbonyl Ru3Se2 nido clusters were prepared in three different ways. The simple dispersion of [Ru3(mu3-Se)2(CO)7(PPh 3)2] via sol gel process produces an inhomogeneous material; by contrast, homogeneous xerogels were obtained by reaction of [Ru3(mu3-Se)2(CO)8(PPh 3)] with functionalised xerogels containing grafted diphenylphosphine moieties and by reaction of [Ru3(CO)12] with a xerogel containing grafted phosphine-selenide groups. The reaction between [Ru3(CO)12] and dodecyldiphenylphosphine selenide led to the formation of four selenido carbonyl clusters, which are soluble in hydrocarbon solvents and can be deposited as thin films from their solution by slow evaporation. Xerogéis de silica contendo carbonilas metálicas polinucleares (clusters) com estrutura nido Ru3Se2 foram preparadas através de três rotas diferentes. A simples dispersão do cluster [Ru3(mi3-Se)2(CO)7(PPh 3)2] pelo processo sol gel produz um material não homogêneo. Xerogéis homogêneos foram obtidos através da reação de [Ru3(mi3-Se)2(CO)8(PPh 3)] com xerogéis funcionalizados contendo fragmentos difenilfosfino enxertados, e pela reação do [Ru3(CO)12] com um xerogel contendo grupos fosfinoseleneto enxertados. A reação entre [Ru3(CO)12] e seleneto de dodecildifenilfosfinoseleneto resultou na formação de quatro clusters contendo ligantes carbonil e seleneto, solúveis em solventes apolares e que podem ser empregados na confecção de filmes

A new type of doubly silylamido-bridged\ud cyclopentadienyl group 4 metal complexes

Doubly bridged di(silyl-η-amido)cyclopentadienyltitanium and -zirconium complexes and their related cations as the [(PhCH 2)B(C 6F 5) 3] - salts have been isolated (see structure of the Ti derivative). The neutral benzylzirconium complex was a very efficient catalyst in the presence of methylaluminoxane for producing high molecular weight polyethylene and ethylene-1-hexene copolymer

Zirconium and hafnium complexes with (allylsilyl)(η-amidosilyl)-η5-cyclopentadienyl ligands: synthesis, structure and reactivity

The disubstituted cyclopentadiene C5H4(SiMe2Cl)[SiMe2(CH2CH=CH2)] was isolated by reaction of the lithium salt [Li{C5H4SiMe2(CH2CH=CH2)}] with SiMe2Cl2. It was then treated with NH2tBu and LiNH(2,6-Me2C6H3) to give the (aminosilyl)cyclopentadienes C5H4[SiMe2(CH2CH=CH2)][SiMe2(NHR)], which were further deprotonated to their dilithium salts [Li2{1-SiMe2NR-3-SiMe2(CH2CH=CH2)C5H3}] (R = tBu, 2,6-Me2C6H3). Reactions of the metal halides ZrCl4(THF)2 and HfCl4 with these dilithium salts, followed by alkylation of the resulting dichloro complexes, afforded the (η1-amidosilyl)-η5-cyclopentadienyl complexes [M{η5-C5H3(SiMe2-η1-NR)[SiMe2(CH2CH=CH2)]}X2] (R = tBu, 2,6-Me2C6H3; X = Cl, Me, CH2Ph; M = Zr, Hf). Only the bis(iminoacyl) complexes [M{η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}{η2-CR=N(2,6-Me2C6H3)}2] (M = Zr, Hf; R = Me, CH2Ph) could be isolated when the dialkylzirconium and -hafnium complexes were treated with CN(2,6-Me2C6H3); these were slowly transformed into the C–C-coupled diazametallacyclopentene compounds [M{η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}{η1-N(2,6-Me2C6H3)-CR=CR-η1-N(2,6-Me2C6H3)}] (R = Me, CH2Ph, M = Zr; R = Me, M = Hf) when their toluene solutions were heated to 70 °C–80 °C for long periods (2–4 d). The structural characterisation of all of the new compounds is described and the molecular structure of the dimeric dichlorozirconocene [ZrCl(μ-Cl){η5-C5H3(SiMe2-η1-NtBu)[SiMe2(CH2CH=CH2)]}]2, was determined by X-ray diffraction methods. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005

Preparation of imido pentamethylcyclopentadienyl molybdenum(IV) complexes. X-ray molecular structure of cis-[MoCp*CI(η-NtBu)]2·C6H6

The reduction of [MoCp * Cl2(NtBu)] 1 with 1 equiv. of 10% sodium amalgam in the presence of CN(2,6-Me2C6H3) yields the green crystalline compound [MoCp * Cl(NtBuCN(2,6-Me2C6H3)] 2 which can be alkylated by MgClMe to give [MoCp * Me(NtBu)CN(2,6-Me2C6H3)] 3. The same reduction in the absence of ligands leads to an almost equimolar mixture of compounds identified as cis- and trans-[MoCp* (μ-Cl)(NtBu)]24 which are slowly and irreversibly transformed into cis-[MoCp * Cl(μ-NtBu)]25 by heating a toluene solution at 90°C. Compounds (cis + trans)-4 and cis-5 are alkylated by MgClMe leading to the same final methyl derivative [MoCp * Me(μ-NtBu)]26, and react with ethylene to yield the adduct [MoCp * Cl(NtBu)(C2H4)] 7. All new complexes were characterized by their analytical composition, IR and NMR spectroscopy and mass spectrometry, and the structure of the benzene solvate of cis-[MoCp * Cl(μ-NtBu)]25 was determined by X-ray diffraction methods.Italian Consiglio Nazionale delle Ricerch

tert-Butylsilylcyclopentadienyl Group 4 metal complexes

New Group 4 metal t-butyldimethylsilylcyclopentadienyl complexes [MCpCp′Cl2] (Cp=η5-C5H5; Cp′=η5-C5H4SiMe2tBu; M=Ti 4, Zr 5, Hf 6) were prepared by reaction of 1 equiv. of the lithium (2) and thallium (3) salts of t-butyldimethylsilylcyclopentadiene 1 with the monocyclopentadienyl complexes [MCpCl3·DME] (M=Zr, Hf) and [TiCpCl3], respectively. A similar reaction using ZrCl4(THF)2 and HfCl4 with 2 equiv. of the lithium salt 2 gave the symmetric [MCp′2Cl2] ( M=Zr 7, Hf 8) metallocenes. Alkylation of these compounds with 2 equiv. of MgRCl (R=Me, CH2Ph) and Li(CH2CMe2Ph) afforded the dialkyl complexes [MCpCp′R2] (R=Me, M=Zr 9, Hf 10; R=CH2Ph, M=Ti 11, Zr 12, Hf 13), [ZrCp′2(CH2Ph)2] 14 and [ZrCpCp′(CH2CMe2Ph)2] 17. A Similar reaction of 5 with 1 equiv. of Mg(CH2Ph)Cl gave the monobenzyl compound [ZrCpCp′Cl(CH2Ph)] (15). Hydrolysis of 15 with a stoichiometric amount of water afforded the dinuclear μ-oxo compound [(ZrCpCp′Cl)2(μ-O)] (16). All of the new complexes reported were characterized by elemental analysis and 1H and 13C NMR spectroscopy and the molecular structures of 4 and 16 were determined by X-ray diffraction methods. Ethylene polymerization activities were measured for compounds 4–7.Financial support of our work by MCyT (project MAT2001-1309) is gratefully acknowledged. R.W. and C.R. are grateful to DFG, MEC and Repsol S.A. for fellowships

Cyclopentadienyl dithiocarbamate and dithiophosphate molybdenum and tungsten complexes

Reactions of [MCp*Cl4] (M=Mo, W; Cp*=η5-C5Me5) with salts of the N,N-diethyldithiocarbamate [Et2dtc]− and O,O′-diethyldithiophosphate [Et2dtp]− anions yield the paramagnetic metal(V) complexes [MCp*Cl3(Et2dtc)] (M=Mo, W) and [MCp*Cl3(Et2dtp)] (M=Mo, W), respectively. Hydrolytic oxidation of both dithiocarbamate–molybdenum complexes with aqueous hydrogen peroxide leads to η2-coordinated peroxo compounds [MoCp*Cl(O–O)O], which were also obtained from [MoCp*Cl4]. The related complexes [MCp′Cl(O–O)O] (M=Mo, Cp′=η5-C5H5; M=W, Cp′=η5-C5Me5) were isolated in a similar way. Reduction of a THF solution of [MoCp*Cl4] with one equivalent of 10% Na/Hg followed by the addition of one equivalent of ammonium dithiophosphate gives [MoCp*Cl2(Et2dtp)] which was also obtained via the reaction of [MoCp*Cl3(Et2dtp)] with MeMgCl, whereas reduction with three equivalents of Na/Hg in the presence of CNtBu leads to the molybdenum(II) complex [MoCp*(Et2dtp)(CNtBu)2] in high yield. All these compounds were characterized by elemental analysis, IR, 1H- and 13C-NMR spectroscopy, magnetic susceptibility measurements and the molecular structures of [Mo(η5-C5H5)Cl(O–O)O] and [Mo(η5–C5Me5)Cl3{η2-S2P(OEt)2}] were determined by X-ray diffraction studies.Consiglio Nazionale delle Ricerche (Rome

Struttura cristallina della catena di μ \mu \ -(oftalato)cuprato(II) di dirubidio diidrato

The crystal structure of dirubidium catena-di- $\mu \$ (ophthalato)cuprate(II) dihydrate has been determined by an X-ray analysis. The structure was solved by Patterson and Fourier methods and refined by block-diagonal least-squares (final R = 6,6%). The structure consists of nearly planar-square complexes formed by four oxygen atoms belonging to four phthalate ions. Each phthalate ion bridges two copper atoms, so the coordination polyhedra are Joined together in chains parallel to [001]