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- Title
Crystalline Diuranium Phosphinidiide and μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores.
- Authors
Rookes, Thomas M.; Gardner, Benedict M.; Balázs, Gábor; Gregson, Matthew; Tuna, Floriana; Wooles, Ashley J.; Scheer, Manfred; Liddle, Stephen T.
- Abstract
Reaction of [U(TrenTIPS)(PH2)] ( 1, TrenTIPS=N(CH2CH2NSiPri3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] ( 2) afforded a rare diuranium parent phosphinidiide complex [{U(TrenTIPS)}2(μ-PH)] ( 3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium μ-phosphido complex [{U(TrenTIPS)}2(μ-P)][K(B15C5)2] ( 4). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] ( 5, 12C4=12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] ( 6) produced the diuranium μ-phosphido complex [{U(TrenTIPS)}(μ-P){U(TrenDMBS)}][Na(12C4)2] [ 7, TrenDMBS=N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.
- Subjects
URANIUM compounds; METAL complexes; ASYMMETRY (Chemistry); CHEMICAL reactions; MATRIX isolation
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 35, p10631
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201706002