Mono(pentamethylcyclopentadienyl)thorium chemistry: Synthesis, structural characterization, and reactivity of aryloxide and alkyl derivatives

Butcher, R J; Clark, D L; Crumbine, S K; Scott, B L; Watkin, J G

doi:10.1021/om9508694

Mono(pentamethylcyclopentadienyl)thorium chemistry: Synthesis, structural characterization, and reactivity of aryloxide and alkyl derivatives

Journal Article · Tue Mar 05 04:00:00 EST 1996 · Organometallics

DOI:https://doi.org/10.1021/om9508694· OSTI ID:226763

Butcher, R J; Clark, D L; Crumbine, S K; Scott, B L; Watkin, J G ^[1]

Los Alamos National Lab., NM (United States)

Reaction of ThBr{sub 4}(THF){sub 4} with 1 equiv of Cp{sup *}MgBr(THF) (Cp{sup *} = {eta}-C{sub 5}Me{sub 5}) produces the mono(pentamethylcyclopentadienyl) complex Cp{sup *}ThBr{sub 3}(THF){sub 3} (1). Treatment of 1 with 1 or 2 equiv of KOAr (Ar = 2,6-t-Bu{sub 2}C{sub 6}H{sub 3}) yields the mono- and bis(aryloxide) species Cp{sup *}ThBr{sub 2}(OAr)(THF) (2) and Cp{sup *}ThBr(OAr){sub 2} (3), respectively. Alkylation of 2 with 2 equiv of Me{sub 3}SiCH{sub 2}MgCl leads to isolation of the bis(alkyl) complex Cp{sup *}Th(OAr)(CH{sub 2}SiMe{sub 3}){sub 2} (4), while 3 reacts with 1 equiv of MeMgBr to form the mono(alkyl)derivative Cp{sup *}ThMe(OAr){sub 2} (5). 4 reacts with dihydrogen to produce the trimeric thorium dihydride [Cp{sup *}ThH{sub 2}(OAr)]{sub 3} (6), while thermolysis of 4 in the presence of triphenylphosphine oxide leads to the isolation of the metallacyclic species Cp{sup *}Th(OC{sub 6}H{sub 3}-t-BuCMe{sub 2}CH{sub 2})(OAr)(O=PPh{sub 3}) (7). In the presence of 1 equiv of [HNMe{sub 2}Ph][(C{sub 6}F{sub 5}){sub 4}], 4 is found to catalyze the hydrogenation of 1-hexene and also the polymerization of ethylene. Compounds 1-7 have been characterized by {sup 1}H NMR and IR spectroscopy, by microanalysis, and, in the case of 3, 4, and 7, by single-crystal X-ray diffraction studies. 29 refs., 3 figs., 4 tabs.

DOE Contract Number:: W-7405-ENG-36

OSTI ID:: 226763

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 5 Vol. 15; ISSN 0276-7333

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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