The high-yield synthesis, spectroscopic and structural determination of three new uranium(IV) and thorium(IV)ate complexes supported by three different diamido ether ligands are reported. The reaction of Li2[2,6-iPr2PhN(CH2CH2)]2O (Li2[DIPPNCOCN]) with 1 equiv. of UCl4 in THF generates [DIPPNCOCN]UCl3Li(THF)2(1), while reaction in toluene/ether gives salt-free [DIPPNCOCN]UCl2.1/2C7H8(2), which was identified by paramagnetically shifted 1H NMR. Reaction of 0.5 equiv. of {[tBuNON]UCl2}2([tBuNON]=[(CH3)3CN(Si(CH3)2)]2O2-) with 3.5 equiv. LiI in toluene and a minimal amount of THF results in [tBuNON]UI3Li(THF)2(3) and is very similar in structure to 1. {[MesNON]ThCl3Li(THF)}2(4), a dimeric complex with a Th2Li2Cl6 core, is prepared by reaction of Li2[2,4,6-Me3PhN(Si(CH3)2)]2O (Li2[MesNON]) with ThCl4 in THF. The analogous reaction in toluene did not yield the salt-free complex but rather a sterically crowded diligated compound, [MesNON]2Th (5), which was also structurally characterized. Complex 5 was prepared rationally by reacting 2 equiv. Li2[MesNON] with ThCl4 in toluene. The reaction of 1 and 3 with 2 equiv. of LiCH2Si(CH3)3 generates the stable, salt-free organoactinides [DIPPNCOCN]U(CH2Si(CH3)3)2(6) and [tBuNON]U(CH2Si(CH3)3)2(7). Complex 6 was structurally characterized. These reactions illustrate the viability of ate complexes as useful synthetic precursors.

The dilithio salts of two chelating diamidosilylether ligands undergo a retro-Brook rearrangement from oxygen to the amido-nitrogen, thereby directly yielding a new mixed-donor amido/amino/siloxo ligand. When reacted with chromium(II), siloxo-bridged dimers and a very strong eta(2)-(N,C(ipso)) arylamido interaction are featured.

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 increasing electron-donating ability of the R substituents, with tau(1/2) values ranging from 5.7 x 10(1) to 1.5 x 10(8) s for 2c and 5c, respectively.

Two-dimensional coordination polymers of AgX (X ‫؍‬ BF 4 ؊ , ClO 4 ؊ ) and 1,4-diazatriphenylene show significant distortions of the polycyclic aromatic ligand and a new unsymmetrical 2 --2 bonding mode for BF 4 ؊ and ClO 4 ؊ .