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

Coles, Martyn P, Hitchcock, Peter B, Khvostov, Alexei V, Protchenko, Andrey, Lappert, Michael F, Li, Zhengning and Protchenko, Andrey V (2010) Crystalline amidocerium(IV) oxides and a side-on bridging dioxygen complex. Dalton Transactions, 39 (29). pp. 6780-6788. ISSN 1477-9226

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Abstract

Complexes [Ce(NR2)(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(NR2)(2)(mu-O)}(n)] (3, n = 2; 4, n = 3), [{Ce(NR ''(2))(2)(mu-O)}(4)] (5), [{(R2N)(3)Ce}(2)(mu-OMOM)] (6, M = Na; 7, M = K), [{(R2N)(3)CeOCe(NR2)(2)}(2)(mu-OKOK)] (8), and [{Ce(NR2)(3)}(2)(mu-eta(2):eta(2)-O-2)]center dot 2C(n)H(2n+2) (9, n = 6; 9', n = 5) [R = SiMe3, NR ''(2) = TMP = NC(Me)(2)(CH2)(3)CMe2]. 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 NaNR2 (8) or KNR2 (7, 8). From 1 and an quivalent portion of 2,6-Bu-t(2)-benzoquinone after 5 weeks in pentane there was obtained the bis(amido)cyclotricer(IV)oxane 4. The NMR spectral solution chemical shifts for NR2 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(NR2)(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(NR2)(3)O}(2)((Bu2C6H2)-Bu-t-1,4)].

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Martyn Coles
Date Deposited: 06 Feb 2012 19:12
Last Modified: 13 Jun 2012 13:18
URI: http://sro.sussex.ac.uk/id/eprint/19562
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