Crystalline amidocerium(IV) oxides and a side-on bridging dioxygen complex.

Complexes [Ce(NR(2))(3)] (1) or [Ce(NR''(2))(3)] (2) were cerium(III) precursors to the X-ray characterised crystalline oligomeric oxygen-containing amidocerium(IV) compounds [{Ce(NR(2))(2)(mu-O)}(n)] (3, n = 2; 4, n = 3), [{Ce(NR''(2))(2)(mu-O)}(4)] (5), [{(R(2)N)(3)Ce}(2)(mu-[upper bond 1 start]OMOM[upper bond 1 end])] (6, M = Na; 7, M = K), [{(R(2)N)(3)CeOCe(NR(2))(2)}(2)(mu-[upper bond 1 start]OKOK[upper bond 1 end])] (8), and [{Ce(NR(2))(3)}(2)(mu-eta(2):eta(2)-O(2))].2C(n)H(2n+2) (9, n = 6; 9', n = 5) [R = SiMe(3), NR''(2) = TMP = [upper bond 1 start]NC(Me)(2)(CH(2))(3)C[upper bond 1 end]Me(2)]. Each was isolated in low, or for 5 very low, yield. Except for 4, the oxidising agent was O(2) at -27 degrees C in hexane (3, 6, 7, 8, 9), pentane (9'), or toluene (5), and a co-reagent for the alkali metal bis(trimethylsilyl)amido(oxy)cerate(iv)s was NaNR(2) (8) or KNR(2) (7, 8). From 1 and an equivalent portion of 2,6-(t)Bu(2)-benzoquinone after 5 weeks in pentane there was obtained the bis(amido)cyclotricer(IV)oxane 4. The NMR spectral solution chemical shifts for NR(2) groups of 3, 4, and 6-9 were consistent with each sample being diamagnetic and hence a Ce(IV) species. A transient amidocerium(IV) superoxide Ce(NR(2))(3)(eta(2)-O(2)) (J), or its TMP analogue, is considered to be the common first-formed intermediate in each case, while 4 is believed to have arisen from the adventitious hydrolysis of [{Ce(NR(2))(3)O}(2)((t)Bu(2)C(6)H(2)-1,4)].