title: 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.
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.
authors.affiliation: Laboratoire de Chimie, Electrochimie Moléculaires et Chimie Analytique, UMR CNRS 6521, Université de Bretagne Occidentale, CS 93837, 6 av. Victor Le Gorgeu, 29238 Brest Cedex 3, France.
authors.forename: Françoise
authors.initials: F
authors.lastname: Conan
authors.forename: Benoît
authors.initials: B
authors.lastname: Le Gall
authors.forename: Jean-Michel
authors.initials: JM
authors.lastname: Kerbaol
authors.forename: Sylvie
authors.initials: S
authors.lastname: Le Stang
authors.forename: Jean
authors.initials: J
authors.lastname: Sala-Pala
authors.forename: Yves
authors.initials: Y
authors.lastname: Le Mest
authors.forename: John
authors.initials: J
authors.lastname: Bacsa
authors.forename: Xiang
authors.initials: X
authors.lastname: Ouyang
authors.forename: Kim R
authors.initials: KR
authors.lastname: Dunbar
authors.forename: Charles F
authors.initials: CF
authors.lastname: Campana