Experimental and computational studies on a three-membered diphosphido thorium metallaheterocycle [η⁵-1,3-(Me₃C)₂C₅H₃]₂Th[η²-P₂(2,4,6-ⁱPr₃C₆H₂)₂]

Abstract

A three-membered diphosphido thorium metallaheterocycle complex was prepared and its reactivity was investigated.

Comparative Insertion Reactivity of CO, CO2, tBuCN, and tBuNC into Thorium– and Uranium–Phosphorus Bonds

“…The Th−O bond lengths of 2.510(3) and 2.500(2) Å are similar to those of the Th aminopolycarboxylate complex 62 63,64 as well as double-insertion products of bis(phosphido) complexes in the literature. 40 Previously, we reported the insertion of t BuNC into the An−P bonds of ( with RNC (R = Me 3 Si, cyclohexyl, 2,6-Me 2 C 6 H 3 ) also yields phosphazaallenes. 37 The analogous product (C 5 Me 5 ) 2 U-(CN t Bu)(η 2 (N,C)-( t BuNCPMes) (5; eq 3) is obtainable in moderate yield (57%) by elimination of free H 2 PMes observed in the 31 P NMR spectrum.…”

Divergent uranium- versus phosphorus-based reduction of Me3SiN3 with steric modification of phosphido ligands

“…24 These complexes impart a mismatch between the hard, electropositive Lewis acidic actinide centre, and the so Lewis basic nature of phosphorus, and have been shown to afford unpredictable and unusual chemistry. [25][26][27][28][29][30][31][32][33][34] We recently showed that the U(III) complex, (C 5 Me 5 ) 2 U(THF) [P(SiMe 3 )(Mes)] reacts with Me 3 SiN 3 to form the U(VI) bis(imido) complex, (C 5 Me 5 ) 2 U(]NSiMe 3 ) 2 . 35 In order to prevent the formation of the bis(imido) complex, here, we used the mixed phosphido-methyl complexes (C 5 Me 5 ) 2 U(CH 3 )[P(SiMe 3 )(R)], R ¼ C 6 H 5 (Ph), 1; 2,4,6-Me 3 C 6 H 2 (Mes), 2.…”

Thorium(IV) and Uranium(IV) Phosphaazaallenes

“…Thus, they are less inclined to form strong interactions with ligands bearing soft-donor atoms such as phosphorus. Therefore, the actinide-phosphido bond should, and has been demonstrated, be relatively reactive [20][21][22][23][24][25][26][27][28][29][30].…”