Bis(eta/sup 8/-1,3,5,7-tetramethylcyclooctatetraene) compounds of protactinium, neptunium, and plutonium

Journal Article · Tue Jul 01 00:00:00 EDT 1980 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50209a075· OSTI ID:5066320

Solar, J P; Burghard, H P.G.; Banks, R H; Streitwieser, A Jr; Brown, D

X-ray powder diffraction patterns have shown that bis(ciclooctatetraene)-actinide(IV) complexes are all structurally and chemically similar. This suggests that the same bonding scheme prevails throughout these actinide(IV)-COT series and the unusual degree of covalency demonstrated by the Moessbauer spectra of Np(RC/sub 8/H/sub 7/)/sub 2/ may be a common property. However, comparisons across the actinide series are hampered by the lack of data on protactium complexes. Therefore, a new study of the synthesis of bis(cyclooctatetraene) protactinium was undertaken. The reaction of the tetramethylcyclooctatetraene dianion (TMCOT/sup 2 -/) with PaCl/sub 4/, gave a light brown solution from which Pa((CH/sub 3/)/sub 4/C/sub 8/H/sub 4/)/sub 2/ can be isolated in low yield. This compound, which has not previously been prepared, was soluble in tetrahydrofurn (THF) and slightly soluble in benzene, and it was identified by its x-ray power diffraction pattern. In addition, a new synthetic route to actinocenes was developed by using neptunium and plutonium borohydride complexes M(BH/sub 4/)/sub 4/. These volatile air-sensitive compounds are readily soluble in organic solvents and were allowed to react with cyclooctatetraene dianions in THF. Np(TMCOT)/sub 2/, which has previously been prepared from NpCl/sub 4/, is readily isolated by recrystallization from THF. X-ray powder patterns show that Pa and Pu complexes are isostructural with Np(TMCOT)/sub 2/.

• Research Organization: Univ. of California, Berkeley
• DOE Contract Number: W-7405-ENG-48
• OSTI ID: 5066320
• Journal Information: Inorg. Chem.; (United States), Vol. 19:7
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
NEPTUNIUM COMPLEXES
CHEMICAL PREPARATION
MOLECULAR STRUCTURE
PLUTONIUM COMPLEXES
PROTACTINIUM COMPLEXES
COMPARATIVE EVALUATIONS
CYCLOALKENES
SPECTROPHOTOMETRY
URANIUM COMPLEXES
VISIBLE SPECTRA
X-RAY DIFFRACTION
ACTINIDE COMPLEXES
ALKENES
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
HYDROCARBONS
ORGANIC COMPOUNDS
SCATTERING
SPECTRA
SYNTHESIS
TRANSURANIUM COMPLEXES
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials