Reactions of 7,7,8,8-Tetracyanoquinodimethane (TCNQ) with Alkynyl-Iron- and -Ruthenium Complexes: Synthesis of Ru{C=CC(CN)=C6H4=C(CN)2}(PPh3)2Cp, a New Donor - Acceptor Molecular Array

Abstract

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.