Experimental and Computational Studies on a Base‐Free Terminal Uranium Phosphinidene Metallocene

Wang, Deqiang; Ding, Wanjian; Hou, Guohua; Zi, Guofu; Walter, Marc D.

doi:10.1002/chem.202003465

Cited by 46 publications

(39 citation statements)

References 147 publications

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“…Moreover, the values of ρ ( r ) at U—N/O BCPs are larger than those at Th—N/O BCPs, respectively, indicating that the former has more covalency compared to the latter. [ 75‐80 ] These results are supported by Wiberg bond indexs (WBIs) presented in Table 2. The frontier molecular orbitals (MOs) of [U(Tren TIPS )(OCP)] and [Th(Tren TIPS )(OCP)] complexes are displayed in Figure 2.…”

Section: Resultssupporting

confidence: 57%

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

Liu

et al. 2021

Chin. J. Chem.

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Uranium | Thorium | Tripodal ligand |Computational chemistry | Electronic structureThe issue of covalence of actinide complexes remains controversial to date. The introduction of 2-phosphaethynolate anion into actinide complexes is expected to investigate the reaction mode and the bonding property. Herein, we describe the functionalization of An(Tren TIPS )Cl (1: An = U; 2: An = Th) precursors with NaOCP(dioxane) 2.5 through salt-elimination method leading to the formation of the corresponding uranium and thorium phosphaethynolate species: [U(Tren TIPS )(OCP)] ( 3) and [Th(Tren TIPS )(OCP)] (4). These two complexes were fully characterized by nuclear magnetic resonance (NMR), FT-IR spectrum, UV-vis-NIR spectroscopies as well as X-ray crystal diffraction. Computational analyses of the two complexes reveal that the U-O bond has a more covalent bond property than the Th-O bond due to more 5f orbital contribution for U.

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Section: Resultssupporting

confidence: 57%

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

Liu

et al. 2021

Chin. J. Chem.

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“…Investigating this concept will afford insight into the fundamental coordination chemistry of these understudied metals as well as the potential to lead to advanced strategies in separation technologies. There are a number of phosphido complexes of thorium and uranium but few examples of arsenido, ,− ,, diphosphido, − diarsenido, , phosphinidiide, ,− arsinidiide, , phosphinidene, ,− and arsinidene, ,, Scheme . Recently, a diuranium complex containing a (P 2 ) 2– unit was reported .…”

Section: Introductionmentioning

confidence: 99%

Systematic Investigation of the Molecular and Electronic Structure of Thorium and Uranium Phosphorus and Arsenic Complexes

et al. 2021

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In continuing to examine the interaction of actinide-ligand bonds with soft donor ligands, a comparative investigation with phosphorus and arsenic was conducted. A reaction of (C 5 Me 5 ) 2 AnMe 2 , An = Th, U, with 2 equiv of H 2 AsMes, Mes = 2,4,6-Me 3 C 6 H 2 , forms the primary bis(arsenido) complexes, (C 5 Me 5 ) 2 An[As(H)Mes] 2 . Both exhibit thermal instability at room temperature, leading to the elimination of H 2 , and the formation of the diarsenido species, (C 5 Me 5 ) 2 An(η 2 -As 2 Mes 2 ). The analogous diphosphido complexes, (C 5 Me 5 ) 2 An(η 2 -P 2 Mes 2 ), could not be synthesized via the same route, even upon heating the bis(phosphido) species to 100 °C in toluene. However, they were accessible via the reaction of dimesityldiphosphane, MesP(H)P(H)Mes, with (C 5 Me 5 ) 2 AnMe 2 at 70 °C in toluene. When (C 5 Me 5 ) 2 AnMe 2 is reacted with 1 equiv of H 2 AsMes, the bridging μ 2 -arsinidiide complexes [(C 5 Me 5 ) 2 An] 2 (μ 2 -AsMes) 2 are formed. Upon reaction of (C 5 Me 5 ) 2 UMe 2 with 1 equiv of H 2 PMes, the phosphinidiide [(C 5 Me 5 ) 2 U(μ 2 -PMes)] 2 is isolated. However, the analogous thorium reaction leads to a phosphido and C−H bond activation of the methyl on the mesityl group, forming {(C 5 Me 5 ) 2 Th[P(H)(2,4-Me 2 C 6 H 2 -6-CH 2 )]} 2 . The reactivity of [(C 5 Me 5 ) 2 An(μ 2 -EMes)] 2 was investigated with OPPh 3 in an effort to produce terminal phosphinidene or arsinidene complexes. For E = As, An = U, a U(III) cation−anion pair [(C 5 Me 5 ) 2 U(η 2 -As 2 Mes 2 )][(C 5 Me 5 ) 2 U(OPPh 3 ) 2 ] is isolated. The reaction of [(C 5 Me 5 ) 2 Th(μ 2 -AsMes)] 2 with OPPh 3 does not result in a terminal arsinidene but, instead, eliminates PPh 3 to yield a bridging arsinidiide/oxo complex, [(C 5 Me 5 ) 2 Th] 2 (μ 2 -AsMes)(μ 2 -O). Finally, the combination of [(C 5 Me 5 ) 2 U(μ 2 -PMes)] 2 and OPPh 3 yields a terminal phosphinidene, (C 5 Me 5 ) 2 U(PMes)(OPPh 3 ), featuring a short U−P bond distance of 2.502(2) Å. Electrochemical measurements on the uranium pnictinidiide complexes demonstrate only a 0.04 V difference with phosphorus as a slightly better donor. Magnetic measurements on the uranium complexes show more excited-state mixing and therefore higher magnetic moments with the arsenic-containing compounds but no deviation from uncoupled U(IV) behavior. Finally, a quantum theory of atoms in molecules analysis shows highly polarized actinide-pnictogen bonds with similar bonding characteristics, supporting the electrochemical and magnetic measurements of similar bonding between actinide-phosphorus and actinide-arsenic bonds.

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“… 5,6 Notably, several uranium-redox active ligand systems have been reported to effect the four-electron reductive cleavage of azobenzene. 5 c , d , h ,6 b , c ,7–11 In particular, uranium( iii )/( iv )-redox active ligands systems such as hydride, 5 e ,7 tetraphenylborate, 5 d ,8 bridging arene, 9 bipyridine, 6 c phosphinidene, 10 and metallacyclopropene 11 complexes reduce azobenzene to yield U( vi ) bis(imido) complexes. Some of these complexes also effect the multielectron reduction of alkynes to yield uranium metallacycles.…”

Section: Introductionmentioning

confidence: 99%

Single metal four-electron reduction by U(ii) and masked “U(ii)” compounds

et al. 2021

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Experimental and Computational Studies on a Base‐Free Terminal Uranium Phosphinidene Metallocene

Cited by 46 publications

References 147 publications

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

Systematic Investigation of the Molecular and Electronic Structure of Thorium and Uranium Phosphorus and Arsenic Complexes

Single metal four-electron reduction by U(ii) and masked “U(ii)” compounds

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