Synthesis, structures, and kinetics of mixed-donor amido-amino-siloxo ligands from symmetrical diamidosilyl ether ligands via a retro-brook rearrangement

Inorganic Chemistry
Farzad HaftbaradaranDaniel B Leznoff

Abstract

Deprotonation of the new (R = propyl, 3,5-Me(2)Ph) and previously prepared (R = 2,4,6-Me(3)Ph, 2,6-(i)Pr(2)Ph, 3,5-(CF(3))(2)Ph) symmetrical diamidosilyl ether ligand precursors {[RNHSiMe(2)](2)O} with 2 equiv of nBuLi in THF resulted in a new class of mixed-donor amido-amino-siloxo ligands of the form {RNLiSiMe(2)N(R)SiMe(2)OLi} (R= propyl (1c), 3,5-Me(2)Ph (2c), 2,4,6-Me(3)Ph (3c), 2,6-(i)Pr(2)Ph (4c), 3,5-(CF(3))(2)Ph (5c)) in one-step and high yield via a retro-Brook-type rearrangement mechanism. Ligands 1c, 3c, and 4c have been structurally characterized in the presence and absence of THF/ether donor solvents and exhibited a range of aggregated structures with ring-laddering, ring-stacking, and cubane motifs; higher-nuclearity clusters for base-free systems were observed for 1c and 4c. 1H, (7)Li, and selected (13)C{(1)H} NMR spectra in THF-d(8) and toluene-d(8) are described; the (7)Li data are indicative of intramolecular fluxional behavior as a function of temperature but do not shed light on the nuclearity of the salts in solution. Reaction kinetics were investigated by variable-temperature 1H NMR spectroscopy and showed that the rate of rearrangement reactions increases with decreasing steric hindrance and with increas...Continue Reading

References

Feb 12, 2000·Angewandte Chemie·R Kempe
Jun 8, 2001·Journal of the American Chemical Society·D B GrotjahnL M Ziurys
Jan 9, 2003·Chemical Reviews·Vernon C Gibson, Stefan K Spitzmesser
Jan 23, 2003·Chemical Communications : Chem Comm·Garry MundDaniel B Leznoff
Oct 21, 2003·Chemistry : a European Journal·Garry MundDaniel B Leznoff
Jul 5, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Farzad HaftbaradaranDaniel B Leznoff

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Citations

Dec 16, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Victoria P Colquhoun, Carsten Strohmann
Nov 22, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Cassandra E Hayes, Daniel B Leznoff

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