Reactions of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with alkynyl-iron or -ruthenium complexes : synthesis of Ru{CC(CN)=C6H4=C(CN)2}(PPh3)2Cp, a new donor acceptor molecular array - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Australian Journal of Chemistry Année : 2012

Reactions of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with alkynyl-iron or -ruthenium complexes : synthesis of Ru{CC(CN)=C6H4=C(CN)2}(PPh3)2Cp, a new donor acceptor molecular array

Résumé

Reactions of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with the alkynyl-iron and ruthenium complexes [M](C≡CR) {[M] = Fe(dppe)Cp*, Ru(PPh3)2Cp; R = H, Ph} are described. The iron complex Fe(C≡CPh)(dppe)Cp* (2a) is oxidized by TCNQ to give the kinetically stable salt [2a*+][TCNQ]*- . Displacement of [TCNQ]*- is achieved by ionic metathesis upon addition of KPF6 to produce [2a*+]PF6. In contrast, Fe(C≡CH)(dppe)Cp* (2b) reacted with TCNQ to give a mixture of compounds containing Fe(=C=CH2)(dppe)Cp* (3a), {Fe(dppe)Cp*}2(μ-C=CHCH=C) (3b), and the zwitterionic complex Fe+{=C=CHC(CN)2C6H4C-(CN)2}(dppe)Cp* (3c). In contrast, the reaction of TCNQ with Ru(C≡CR)(PPh3)2Cp (4a, R = Ph; 4b, R = H) gave selectively the zwitterionic vinylidenes Ru+{=C=CRC(CN)2C6H4C-(CN)2}(PPh3)2Cp (5a, R = Ph; 5b, R = H), in which the Ru centres are positively charged and the counter-anion is located on the further C(CN)2 group. On heating 5b, elimination of HCN affords Ru{C≡CC(CN)=C6H4=C(CN)2}(PPh3)2Cp (1), while similar treatment of 5a gives Ru{η3-C(CN)2CPh=C6H4=C(CN)2}(PPh3)Cp (6) with loss of PPh3. X-ray structures of 1, 5a, and 6, cyclic voltammetry, and UV-vis spectroscopy of 1 provided evidence for the electronic structures of the new complexes.
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hal-00836771 , version 1 (21-06-2013)

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Michael I. Bruce, Alexandre Burgun, Guillaume Grelaud, Claude Lapinte, Brian W. Skelton, et al.. Reactions of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with alkynyl-iron or -ruthenium complexes : synthesis of Ru{CC(CN)=C6H4=C(CN)2}(PPh3)2Cp, a new donor acceptor molecular array. Australian Journal of Chemistry, 2012, 65 (7), pp.763-772. ⟨10.1071/CH11493⟩. ⟨hal-00836771⟩
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