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https://hdl.handle.net/2440/74384
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Type: | Journal article |
Title: | 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 |
Other Titles: | Reactions of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with alkynyl-iron- and -ruthenium complexes: synthesis of Ru{C=CC(CN)=C(6)H(4)=C(CN)(2)}(PPh(3))(2)Cp, a new donor-acceptor molecular array |
Author: | Bruce, M. Burgun, A. Grelaud, G. Lapinte, C. Skelton, B. Zaitseva, N. |
Citation: | Australian Journal of Chemistry: an international journal for chemical science, 2012; 65(7):763-772 |
Publisher: | C S I R O Publishing |
Issue Date: | 2012 |
ISSN: | 0004-9425 1445-0038 |
Statement of Responsibility: | Michael I. Bruce, Alexandre Burgun, Guillaume Grelaud, Claude Lapinte, Brian W. Skelton, and Natasha N. Zaitseva |
Abstract: | <jats:p>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.</jats:p> |
DOI: | 10.1071/CH11493 |
Published version: | http://dx.doi.org/10.1071/ch11493 |
Appears in Collections: | Aurora harvest 4 Chemistry publications |
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