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

Hörger C, Heinemann FW, Louyriac E, Maron L, Gruetzmacher H, Meyer K (2017)

Publication Status: Published

Publication Type: Journal article

Publication year: 2017

Journal

Organometallics American Chemical Society

Publisher: AMER CHEMICAL SOC

Book Volume: 36

Pages Range: 4351-4354

Journal Issue: 22

DOI: 10.1021/acs.organomet.7b00590

Abstract

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.

Authors with CRIS profile

Christopher Hörger Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Université Fédérale de Toulouse Midi-Pyrénées FR France (FR) Eidgenössische Technische Hochschule Zürich (ETHZ) / Swiss Federal Institute of Technology in Zurich CH Switzerland (CH)

How to cite

APA:

Hörger, C., Heinemann, F.W., Louyriac, E., Maron, L., Gruetzmacher, H., & Meyer, K. (2017). Formation of a Uranium-Bound eta(1)-Cyaphide (CP-) Ligand via Activation and C-O Bond Cleavage of Phosphaethynolate (OCP-). Organometallics, 36(22), 4351-4354. https://dx.doi.org/10.1021/acs.organomet.7b00590

MLA:

Hörger, Christopher, et al. "Formation of a Uranium-Bound eta(1)-Cyaphide (CP-) Ligand via Activation and C-O Bond Cleavage of Phosphaethynolate (OCP-)." Organometallics 36.22 (2017): 4351-4354.

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