0000000000049713
AUTHOR
Patrice Perron
Synthesis of bis(diphenylphosphinocyclopentadienyl) yttrium chloride complexes and heterodimetallic derivatives. X-ray structure of bis[(μ-chloro)bis(diphenylphosphinocyclopentadienyl) yttrium(III)]
Abstract Reaction of lithium diphenylphosphinocyclopentadienide with YCl 3 or YCl 3 (THF) 3 and working lead to the formation of three yttrocene phosphines: the lithium metal adduct isolated as (Ph 2 PC 5 H 4 ) 2 Y(μ-Cl) 2 Li(THF) 2 · 0.5 LiCl ( 1 ), the chloride-bridged dimeric species {(Ph 2 PC 5 H 4 ) 2 Y(μ-Cl)} 2 ( 2 ), and the coordinated monometal species [(Ph 2 PC 5 H 4 ) 2 YCl(THF)] ( 3 ). The X-ray structure of 2 is remarkable in that the crystal exhibits two independent chloride-bridged dimers that differ in the arrangement ( syn, anti ) of the diphenylphosphino groups. Chelation of phosphorus atoms to a molydenum carbonyl moiety is also reported.
Placental DNA methylation signatures of maternal smoking during pregnancy and potential impacts on fetal growth.
We would like to thank all the families that participated in these studies for their generous contribution. Detailed acknowledgements and funding can be found in Sup plementary Material.
Group 4 and Group 8 unbridged metallocene derivatives with a pendant fluorenyl group. X-ray structure of 1,1â²-bis[2-(2-fluorenyl)propyl]ferrocene
Abstract The action of one equivalent of BuLi on 2-cyclopentadienyl-2-fluorenylpropane (C5H5CMe2C13H9) led to the monoanionic salt LiC5H4CMe2C13H9. This anion was reacted with Fe2Cl4(THF)3, TiCl3(THF)3, ZrCl4, HfCl4 or CpZrCl3, DME and, in a mixture with CpLi, with Fe2Cl4(THF)3 affording the corresponding metallocenes and metallocene dichlorides. The X-ray structure of Fe(η5-C5H4CMe2C13H9)2 is described. The first results about the reactivity of the fluorenyl group are reported together with the synthesis of Zr(η5-C5H5)[η5-C5H4CMe2-η5-C13H8Rh(cod)]Cl2, which has been tested using hydroformylation and cyclotrimerisation catalysis.
Novel group 4b ansa-metallocene complexes with the shortest bridge: [1,1′-isopropylydene-3,3′-di-t.Bu-bis(η5-cyclopentadienyl)] Ti and Zr dichlorides
Abstract Reaction of [1,1′-isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienide)] dilithium with TiCl3, followed by treatment with HCl, and ZrCl4 in various solvent mixtures in the temperature range 0–50°C gives corresponding ansa-metallocene dichlorides as mixtures of the anti/syn-isomers, 1:1. The crystal and molecular structures of three of the four isomers were determined, i.e. rac(anti)-[1,1′-isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienyl)]TiCl2, space group B2/b, rac(anti)-[1,1′-isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienyl)]ZrCl2, space group P212121, and meso(syn)-1,1′-[isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienyl)]ZrCl2, space group P21/n.