title: Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O zirconium(IV) complexes.
abstract: The reactivity of the geminal dianion of tetraisopropyl methylenediphosphonate, 3, with [ZrCl4(THF)2] affords a trinuclear structure 5 in which an unprecedented triscarbene-Zr dianionic fragment is found. The overall trinuclear arrangement is assembled by PO bridging moieties. The X-ray crystal structure of 5 is presented. The reaction of complex 5 with stoichiometric amounts of pyridine affords a dinuclear complex 6 whose formulation was ascertained by an X-ray crystal structure. Complexes 5 and 6 cleanly react with aldehydes (R1)(H)CO to afford the corresponding olefin of general formula [((OiPr)2P=O)2C=C(R1)(H)]. DFT calculations which were carried out on the model complex of 5t and a hypothetical monometallic Zr complex [Zr(3)Cl2(OMe2)2] 8t indicate that the Zr-C bond only features a weak pi-interaction between the carbon atom and a vacant orbital at the metal. The polarization of the orbital towards the carbon center is consistent with the observed nucleophilic character of the carbene complexes described here.
authors.affiliation: Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, 91128, Palaiseau Cédex, France.
authors.forename: Hadrien
authors.initials: H
authors.lastname: Heuclin
authors.forename: Dan
authors.initials: D
authors.lastname: Grünstein
authors.forename: Xavier-Frederic
authors.initials: XF
authors.lastname: Le Goff
authors.forename: Pascal
authors.initials: P
authors.lastname: Le Floch
authors.forename: Nicolas
authors.initials: N
authors.lastname: Mézailles