Ca[(Ph₂PO)₂N]₂·nTHF, an α-hydroperoxidation promoter of coordinated THF molecules

Article type: Research Article

Authors: Morales-Juárez, Jesús | Cea-Olivares, Raymundo | Moya-Cabrera, Monica | García-Montalvo, Veronica | Toscano, Ruben A.

Affiliations: Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México, 04510, D.F., México

Note: [] Corresponding author. E-mail: cea@servidor.unam.mx

Abstract: Ca[(Ph2PO)2N]2·nTHF (2) was obtained by direct synthesis from tetraphenylimidodiphosphinic acid and Ca° in THF. X-ray quality single crystals of Ca2[(Ph2PO)2N]4·H2O (3) and Ca[(Ph2PO)2N]2·2C4H8O3 (4) were obtained upon crystallization of 2 under different conditions. The solid-state structure of 3 reveals a Ca2O3 core in which the two hexacoordinated calcium metals are linked together by three µ-oxygen atoms from three independent tetraphenylimidodiphosphinate ligands. Compound 4 is a monomeric octahedral complex bearing two tetraphenylimidodiphosphinate ligands in the equatorial plane and two α-hydroperoxidated THF molecules, formed in situ, in the axial positions. Compound 4 represents the first example of a metal center exhibiting this type of hydroperoxidation behavior.

Keywords: Calcium, Imidodiphosphinate, Hydroperoxidation

DOI: 10.1080/10241220500070711

Journal: Main Group Chemistry, vol. 4, no. 1, pp. 23-31, 2005