RESUMO
A new 'diphosphazidosalen' ligand was synthesized and successfully transferred to uranium using salt metathesis strategies. The resultant 8-coordinate uranium(iv) diphosphazide complex [κ6-1,2-{(N3)PPh2(2-O-C6H4)}2C6H4]UCl2 (1) is unstable to consecutive N2 loss, affording the asymmetric species [κ5-1-{(N3)PPh2(2-O-C6H4)}-2-{N=PPh2(2-O-C6H4)}C6H4)]UCl2 (2), defined by a phosphazide-phosphinimine mixed-ligand framework, and ultimately, the uranium(iv) phosphasalen complex [κ4-1,2-{N=PPh2(2-O-C6H4)}2C6H4]UCl2(THF) (3).
RESUMO
Palladium-catalyzed coupling of 1-adamantylamine (2 equiv.) with 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylxanthene afforded the proligand 4,5-bis(1-adamantylamino)-2,7-di-tert-butyl-9,9-dimethylxanthene, H2[XAd] (1), which upon deprotonation with excess KH or KCH2Ph in THF or dme generated [{K(THF)3}2(XAd)] (2a) and [K2(XAd)(dme)] (2b). Subsequent reaction of in situ generated 2a or 2b with [ThCl4(dme)2] yielded [(XAd)ThCl4K2]·x(dme) (3; x = 0.5-2), which reacted with 2 equiv. of LiCH2SiMe3 or K[allylTMS] to afford the bis(hydrocarbyl) complexes [(XAd)Th(CH2SiMe3)2(THF)] (4) and [(XAd)Th(η3-allylTMS)2] {5; allylTMS = 1-(SiMe3)C3H4}. Dialkyl complex 4 was stable at 80 °C for at least 2.5 hours, but decomposed over 4.5 hours at 110 °C. Diallyl complex 5 was stable for hours at 85 °C, and suffered less than 5% decomposition after 10 minutes at 155 °C. At room temperature, averaging of the syn and anti protons of the allyl CH2 groups of 5 occurred on the NMR timescale, as a consequence of rapid π-σ-π hapticity changes. Additionally, low temperature 1H and 13C NMR spectroscopy indicates that 5 exists as a rapidly exchanging mixture of two isomers with C1 and C2 symmetry. Compounds 2a, 4 and 5 were crystallographically characterized.
