Formation of a Uranium-Bound eta(1)-Cyaphide (CP-) Ligand via Activation and C-O Bond Cleavage of Phosphaethynolate (OCP-)

Christopher J. Hoerger , Frank W. Heinemann , Elisa Louyriac (1) , Laurent Maron (1) , Hansjoerg Gruetzmacher (2) , Karsten Meyer (3)

1 LPCNO - Laboratoire de physique et chimie des nano-objets
2 D-CHAB - Department of Chemistry and Applied Biosciences [ETH Zürich]
3 ICMM - Inorganic Chemistry, Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM)

Reaction of the trivalent uranium complex [(((ArO)-Ar-Ad,Me)(3)N]U(DME)] with [Na(OCP)(dioxane)(2.5)] and 2.2.2 -crypt yields the mu-oxo-bridged, diuranium complex [Na(2.2.2-crypt)]-[\(((ArO)-Ar-Ad,Me)(3)N)U(DME)\(mu-O)\(((ArO)-A r-Ad,Me)(3)N)U(CP)\] (1). Complex 1 features an asymmetric, dinuclear U-IV-O-U-IV core structure with a cyaphide (CP-) anion eta(I)-CP bound to one of the U ions, and a kappa(2)-O DME coordinated to the other. The CP- ligand is unprecedented in uranium chemistry and is formed through reductive C-O bond cleavage of the phosphaethynolate anion (OCP-). An analogous reaction was performed starting from the tetravalent uranium halide complex [(((ArO)-Ar-Ad,Me)N-3)U(DME)(C1)]. This salt metathesis approach with 2.70 [Na(OCP)(dioxane)(2.5)] results in formation of the mononuclear complex [(((ArO)-Ar-Ad,Me)(3)N)U(DME) (OCP) (2) with an OCP- anion bound to the uranium(IV) center via the oxygen atom in an eta(1)-OCP fashion.

Domaines: Physique [physics]; Chimie

Christopher J. Hoerger, Frank W. Heinemann, Elisa Louyriac, Laurent Maron, Hansjoerg Gruetzmacher, et al.. Formation of a Uranium-Bound eta(1)-Cyaphide (CP-) Ligand via Activation and C-O Bond Cleavage of Phosphaethynolate (OCP-). Organometallics, 2017, 36 (22), pp.4351--4354. ⟨hal-01961156⟩