Diphosphinoamido complexes of thorium(IV) and uranium-(IV) and -(V). Crystal structures of [{ThCl2[N(CH2CH2PPri 2)2]2}2] and [{UCl2[N(CH2CH2PEt2)2]2}2]

Abstract

Diphosphinoamido Complexes of Thorium(iv) and Uranium-(iv) and =(v). Crystal Structures of [{ThC12[N(CH2CH2PPri2)2]2}2]and [WCI,"( CH2C H2PEt2),12),1 t

Pentavalent uranium chemistry—synthetic pursuit of a rare oxidation state

“…of the 16)). 69,70 The solution magnetic moment for 82 (m eff = 1.61 m B /U) is similar to those values obtained for the U V -halide complexes 2 and is consistent with the complex possessing a 5f 1 U V metal center.…”

Synthesis and characterization of phosphine adducts of thorium borohydride, Th(BH4)4

“…In fact, thorium can form phosphine complexes as shown in the 1980s by Andersen, who prepared a series of ThX 4 (dmpe) 2 complexes where dmpe is 1,2-bis(dimethylphosphino) ethane and X is halide, alkyl, or alkoxide [5,6]. Since then, however, only a few other thorium phosphine complexes have been described: Cp 2 ThX 2 (dmpe), where X is halide, alkyl, or alkoxide [7,8]; the mixed phosphinophosphide Th[P(CH 2 CH 2 PMe 2 ) 2 ] 4 and its CO insertion product [9]; and phosphinoamide complexes of stoichiometry ThCl x [N(CH 2 CH 2 PR 2 ) 2 ] 4 À x , where x ¼ 1e3 [9]. Although competitive binding studies show that trivalent actinides bind phosphines in preference to amines [10], there have been no comparable studies of tetravalent actinides.…”

“…e3.105(2) Å in Th[P(CH 2 CH 2 PMe 2 ) 2 ] 4 [16e18], and 3.116(4) and 3.207(5) Å in ThCl 2 {N(CH 2 CH 2 PPr i 2 ) 2 } 2[9]. In 3, the four Th/B distances fall into two quite distinct sets: groups bound in a k 3 fashion, whereas the latter are k 2 .…”

Influence of the Nature of the Ligands on the Electronic Ground State of Organouranium(V) Compounds, Studied by Electron Paramagnetic Resonance

“…In this case the g-factors of U(V) may theoretically vary between 2.00 and -1.43, with experimental values mostly in the range -0.2 to -0.7. 4 More recently, some pentavalent uranium complexes with metal-nitrogen bonds have been synthesized: the complex (MeC 6 H 4 C{NSiMe 3 } 2 ) 2 UCl 3 , 5 the two bis(trimethylsilyl)amide complexes [{(Me 3 Si) 2 N} 3 UX] (X ) O or NR), 6 and the phosphino amide complex [{(R 2 PCH 2 CH 2 ) 2 N} 3 UCl 2 ] (R ) Et, i-Pr); 7 the latter gave a very weak EPR signal (g ) 2.0039) at 77 K, but this free electron spin line could also be due to a radical impurity. The EPR spectrum of the cationic bis-(porphyrin)uranium(IV) complex [(TPP) 2 U][SbCl 6 ] (TPP ) tetraphenylporphyrin) 8 is characterized by an axial g-tensor with g | ) 3.175 and g ⊥ ) 1.353.…”