US EPA

4696126 

Journal Article 

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

Hoerger, CJ; Heinemann, FW; Louyriac, E; Maron, L; Gruetzmacher, H; Meyer, K 

2017 

1 

Organometallics
ISSN: 0276-7333
EISSN: 1520-6041 

36 

22 

4351-4354 

10.1021/acs.organomet.7b00590 

WOS:000416614700005 

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)-Ar-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.