Biomedical subjects
Publications and source records attributed to Jered C Garrison.
The reaction of 4-ethynyl-pyridine with tert-butyl lithium followed by its addition to (Me3tacn)RhCl3 affords the facial octahedral complex (Me3tacn)Rh(CCPy)3, condensation of which with the square planar complex cis-(DCPE)Pt(NO3)2 results in a self-assembled trigonal bipyramidal cage with Rh(III) and Pt(II) atoms occupying the vertices.
Addition of AgBF4 or Ag(O3SCF3) to the tripodal ligand, Me3tacnRh(CCPh)3, yields a paddlane complex as well as a novel trinuclear silver "tweezer" complex based upon silver acetylene coordination chemistry. The paddlane is composed of two Me3tacnRh(CCPh)3 moieties held together by silver acetylene interactions. The tweezer complex is composed of one tripodal moiety with three silver atoms coordinated to each acetylene-Rh-acetylene face. The tweezer complex is stabilized by additional interactions, including a triflate anion which serves to cap the complex.
Explore the source record for details and available documents.
Bis(eta5-cyclopentadienyl)[rel-(1R,5S,7R,14S)-(1,3,5,7,9,11,14-heptacyclopentyl-7,14-dioxidotricyclo[7.3.3(1,9).1(5,11)]heptasiloxan-3-yloxy)bis(pentafluorophenyl)borane2-]zirconium, [Zr(C5H5)2(C47H63BF10O12Si7)], consists of [ZrCp2] (Cp is cyclopentadienyl) and [(C6F5)2B] moieties bound to a silsesquioxane core. The silsesquioxane binds to the Zr atom through two of its O atoms to form a distorted tetrahedron. The [(C6F5)2B] moiety is bound to the silsesquioxane through an O atom, forming an Si-O-B bond angle of 168.4 (4) degrees. The steric and electronic effects of the Zr atom and the borate moieties force the silsesquioxane core to distort. These distortions can be seen by examination of the Si-O-Si bond angles.
The binding of H2O to MeAl(OAr)2 (1: Ar = 2,6-di-tert-butyl-4-methylphenyl) in THF-d8 at -40 degrees C provides aquo complex 2, the structure of which was determined by X-ray crystallography. Complex 2 is unstable above 0 degrees C in THF-d8 and decomposes to form ArOH (major), CH4 (minor), and a methyl aluminoxane of undetermined structure. Decomposition of 2 follows first-order kinetics with k = 3.0 x 10-4 s-1 at 5 degrees C. The hindered phenol ArOH slowly reacts with [Cp2ZrMe][MeB(C6F5)3] (4) in bromobenzene-d5 solution at 25 degrees C to furnish CH4 and [Cp2ZrOAr][MeB(C6F5)3] (5), the structure of which was confirmed by X-ray crystallography. This reaction follows second-order kinetics for [ArOH] = [4] = 0.045 M and with k = 2.8 x 10-3 M-1 s-1 at 25 degrees C. This corresponds to a rate that is >107 x slower than the apparent rate of ethylene insertion for 4 at 25 degrees C at typical concentrations encountered in olefin polymerization. The kinetic data, as well as control experiments involving the addition of ArOH to active catalyst producing poly(ethylene), demonstrate that ArOH has essentially no effect on polymerization kinetics involving 4.