Synthesis and characterization of Group 4 organometal oxide complexes

Technical Report · Fri Jan 01 04:00:00 EST 1988

DOI:https://doi.org/10.2172/6181619· OSTI ID:6181619

Babcock, L. M.

The organometallic substituted Keggin polyoxoanions (/eta//sup 5//minus/C/sub 5/(CH/sub 3/)/sub 5/)MPW /sub 11/O/sub 39/((n/minus/C/sub 4/H/sub 9/)/sub 4/N)/sub 4/, M = Ti(1), Zr(2), or HF(3), were prepared by reaction of (/eta//sup 5//minus/C/sub 5/(CH/sub 3/)/sub 5/)MCl/sub 3/ with the lacunary Keggin heteropolyanion ..cap alpha../minus/H/sub 3/PW/sub 11/O/sub 39/((n/minus/C/sub 4/H/sub 9/)/sub 4/N)/sub 4/. Infrared data indicated that complexes 2 and 3 have a normal Keggin structure however complex 1 has a distorted structure. Based-assisted hydrolysis of (/eta//sup 5//minus/C/sub 5/(CH/sub 3/)/sub 5/)MCl/sub 3/, M = Zr or Hf in THF solution gave /(/eta//sup 5//minus/C/sub 5/(CH/sub 3/)/sub 5/)MCl//sub 3/O(OH)/sub 3/Cl, M = Zr(4) or Hf(5), and /(/eta//sup 5//minus/C/sub 5/(CH /sub 3/)/sub 5/)MCl//sub 3/O(OH)/sub 4/, M = Zr(6) or Hf(7). The crystal structure of 6, determined by Dr. Victor Day at Crystalytics Company in Lincoln, NB, revealed a trimer of metals capped on one side by an oxygen atom and on the other side by a hydroxyl ligand with the three edges bridged by hydroxyl ligands. The hydrolysis of (/eta//sup 5//minus/C/sub 5/(CH/sub 3/)/sub 5/)TiCl/sub 3/ resulted in the formation of a six membered titanium oxygen ring /(/eta//sup 5//minus/C/sub 5/(CH/sub 3/)/sub 5/)TiClO//sub 3/, 8. Hydrolysis in the presence of base has produced a tetrameric ligand stabilized titanoxane complex, /(/eta//sup 5//minus/C/sub 5/(CH/sub 3/)/sub 5/)Ti//sub 4/O/sub 6/, 9. 140 refs., 20 figs., 7 tabs.

• Research Organization: Illinois Univ., Urbana (USA)
• DOE Contract Number: AC02-76ER01198
• OSTI ID: 6181619
• Report Number(s): DOE/ER/01198-T34; ON: DE89010944
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMICAL SHIFT
COMPLEXES
CRYSTAL STRUCTURE
DECOMPOSITION
FURANS
HETEROCYCLIC COMPOUNDS
HYDROLYSIS
INFRARED SPECTRA
LIGANDS
LYSIS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
SOLVOLYSIS
SPECTRA
SYNTHESIS
TETRAHYDROFURAN
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
ZIRCONIUM COMPLEXES