Sterically demanding aryloxides as supporting ligands in organoactinide chemistry. Synthesis, structural characterization, and reactivity of Th(O-2,6-t-Bu{sub 2}C{sub 6}H{sub 3}){sub 2}(CH{sub 2}SiMe{sub 3}){sub 2} and formation of the trimeric thorium hydride Th{sub 3}H{sub 6}(O-2,6-t-Bu{sub 2}C{sub 6}H{sub 3}){sub 6}
- Los Alamos National Lab., NM (United States)
Reactions of ThBr{sub 4}(THF){sub 4} with 2 equiv of KOAr (Ar = 2,6-t-Bu{sub 2}C{sub 6}H{sub 3}) produces the bis-(aryloxide) complex ThBr{sub 2}(OAr){sub 2}(THF){sub 2}(1) in 67% yield. Alkylation of 1 with 2 equiv of Me{sub 3}SiCH{sub 2}MgCl allows the isolation of Th(OAr){sub 2}(CH{sub 2}SiMe{sub 3}){sub 2} (2) in 61% yield. Thermolysis of 2 (benzene, 60{degree}C, 36 h) in the presence of NEt{sub 3} results in the formation of the cyclometalated ligand redistribution product Th(OC{sub 6}H{sub 3}-t-BuCMe{sub 2}CH{sub 2})(OAr){sub 2} (3). Reaction of 2 with 1 equiv of 2,6-dimethylphenyl isocyanate leads to insertion into the Th-C bond to yield (ArO){sub 2}Th[C(=NR)CH{sub 2}SiMe{sub 3}] (CH{sub 2}SiMe{sub 3}) (4; R = 2,6-Me{sub 2}C{sub 6}H{sub 3}). Aminolysis of 2 with 2 equiv of 2,6-diisopropylaniline allows the isolation of the bis(amido) species TH(OAr){sub 2}(NH-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 2} (5) in 92% yield. 2 reacts with dihydrogen (1.5 atm) over a period of 7 days to form the trimeric dihydride complex Th{sub 3}({mu}{sub 3}-H){sub 2}({mu}{sub 2}-H){sub 4}(OAr){sub 6} (6). In the presence of 1 equiv of [HNMe{sub 2}Ph][B(C{sub 6}F{sub 5}){sub 4}], 2 catalyzes the hydrogenation of 1-hexene (N{sub t} = 1 h{sup -1}), while 6 is found to be a single-component catalyst for the analogous process (N{sub t} = 3 h{sup -1}). Complexes 1-6 have been characterized by {sup 1}H NMR and IR spectroscopy, microanalysis, and, in the case of 2 and 6, by single-crystal X-ray diffraction studies. Results are presented in this paper. 45 refs., 2 figs., 5 tabs.
- DOE Contract Number:
- W-7405-ENG-36
- OSTI ID:
- 219655
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 3 Vol. 15; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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