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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 [Mo 2(O2CCMe3)3((NC) 2CC(CN)CONH)]∞

Abstract : Under strictly anhydrous conditions, no reaction occurs between Mo 2(O2CCMe3)4 and tetracyanoethylene, TCNE, at room temperature, but after addition of 1 equiv of water, a reaction proceeds to form [Mo2(O2CCMe3) 3((NC)2-CC(CN)CONH)], 1. The compound contains a quadruple-bonded Mo2 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 CH2Cl2 consist of a two-dimensional network, and crystals grown from a C6H6 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 Mo2 unit with no charge transfer. The coordinated TC3A ligand exhibits redox properties similar to those of free TCNE.
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https://hal.univ-brest.fr/hal-01763873
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Submitted on : Wednesday, April 11, 2018 - 2:58:24 PM
Last modification on : Thursday, November 29, 2018 - 4:09:14 PM

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Françoise Conan, B. Le Gall, J.-M. Kerbaol, S. Le Stang, J. Sala-Pala, et al.. 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 [Mo 2(O2CCMe3)3((NC) 2CC(CN)CONH)]∞. Inorganic Chemistry, American Chemical Society, 2004, 43 (12), pp.3673-3681. ⟨10.1021/ic0351186⟩. ⟨hal-01763873⟩

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