Electrochemical, spectroscopic, and structural evidence for the mild hydrolysis of tetracyanoethylene, TCNE, to form the 2,3,3-tricyanoacrylamidate ligand: isolation of an unexpected quadruply-bonded polymeric material [Mo2(O2CCMe3)3((NC)2CC(CN)CONH)]infinity. Academic Article uri icon

abstract

  • Under strictly anhydrous conditions, no reaction occurs between Mo(2)(O(2)CCMe(3))(4) and tetracyanoethylene, TCNE, at room temperature, but after addition of 1 equiv of water, a reaction proceeds to form [Mo(2)(O(2)CCMe(3))(3)((NC)(2)CC(CN)CONH)], 1. The compound contains a quadruple-bonded Mo(2) unit and the 2,3,3-tricyanoacrylamidate anion as a ligand (TC3A), a very unusual hydrolyzed form of TCNE. Two different solid-state structures were obtained after crystallization of 1. Crystals obtained from CH(2)Cl(2) consist of a two-dimensional network, and crystals grown from a C(6)H(6) solution form a 1-D chain motif. In both cases, the TC3A ligand acts as a polydentate ligand involving a bidentate OCN bridging unit and two CN groups. The electrochemical and spectroscopic (IR, UV/vis/near-IR, NMR, EPR) properties of 1 support the formulation in solution as a discrete 1:1 complex of the TC3A donor ligand and a Mo(2) unit with no charge transfer. The coordinated TC3A ligand exhibits redox properties similar to those of free TCNE.

published proceedings

  • Inorg Chem

author list (cited authors)

  • Conan, F., Le Gall, B., Kerbaol, J., Le Stang, S., Sala-Pala, J., Le Mest, Y., ... Campana, C. F.

citation count

  • 18

complete list of authors

  • Conan, Françoise||Le Gall, Benoît||Kerbaol, Jean-Michel||Le Stang, Sylvie||Sala-Pala, Jean||Le Mest, Yves||Bacsa, John||Ouyang, Xiang||Dunbar, Kim R||Campana, Charles F

publication date

  • June 2004