Abstract
The synthesis of tetravalent thorium and uranium complexes with the phosphaazaallene moiety, [N(tBu)C=P(C6H5)]2−, is described. The reaction of the bis(phosphido) complexes, (C5Me5)2An[P(C6H5)(SiMe3)]2, An = Th, U, with two equivalents of tBuNC produces (C5Me5)2An(CNtBu)[η2-(N,C)-N(tBu)C=P(C6H5)] with concomitant formation of P(SiMe3)2(C6H5) via silyl migration. These complexes are characterized by NMR and IR spectroscopy, as well as structurally determined using X-ray crystallography.
Highlights
At 58.5 ppm, while the 13C{1H} NMR spectrum showed a resonance at 265.4 ppm. These resonances are both shifted downfield from the other phosphaazaallene complexes, (C5Me5)2Th(C≡NtBu)[η2N(tBu)C=P(R)], R = Mes, Tipp, which have 31P NMR resonances located at −10.7 ppm and −21.3 ppm, respectively
Despite being secondary phosphido complexes, silyl migration from one phosphido to the other to form the parent phosphine and phosphaazaallene moieties was observed in analogy to the reactivity observed previously with primary phosphido complexes
X-ray quality crystals of 4 were grown from a concentrated pentane solution at −45 ◦C
Summary
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