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)]∞ 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.

author list (cited authors)

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

publication date

  • January 1, 2004 11:11 AM