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Updated: Jun 17, 2026
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Phosphorus stabilized carbene complexes: bisphosphonate dianion synthesis, reactivity and DFT studies of O~C~O
Hadrien Heuclin1, Dan Grünstein, Xavier-Frederic Le Goff
1Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, 91128, Palaiseau Cédex, France.
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.
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