Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes. Issue 15 (29th March 2019)

• Record Type: Journal Article
• Authors: Arnold, Polly L.; Puig-Urrea, Laura; Wells, Jordann A. L.; Yuan, Dan; Cruickshank, Faye L.; Young, Rowan D.
• Is Part Of: Dalton transactions. Volume 48:Issue 15(2019)
• Page Start: 4894
• Page End: 4905
• Publication Date: 2019-03-29
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt05051a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The boroxide ligand [OBAr2 ] − (Ar = Mes, Trip) is shown to be able to support both U III and U IV centres for the first time. Abstract : The boroxide ligand [OBAr2 ] − (Ar = Mes, Trip) is shown to be able to support both U III and U IV centres for the first time. The synthesis and structures of homoleptic and heteroleptic U III and U IV complexes are reported. The UX3 complex with larger substituents, [U(OBTrip2 )3 ]2, exhibits greater thermal stability compared to less encumbered [U(OBMes2 )3 ]2 but reacts with a smaller range of the small molecules tested to date. Initial studies on their capacity to participate in small molecule chemistry show that dark purple [U(OBMes2 )3 ]2 binds and/or reductively activates a variety of small molecules such as pyridine-oxide, triphenylphosphineoxide, sulfur, and dicyclohexylcarbodiimide. While [U(OBMes2 )3 ]2 shows no reaction with CO or CO2, [U(OBTrip2 )3 ]2 is oxidised by both, in the former case forming [U(OBTrip2 )4 ], and in the latter case forming a small quantity of the structurally characterised μ-carbonate product [(μ-CO3 ){U(OBTrip2 )3 }2 ].