The reactions of some σ-alkynylnickel complexes with 7,7,8,8-tetracyanoquinodimethane

Butler, Peter J.; Manning, A. R.; McAdam, C. John

doi:10.1016/j.jorganchem.2007.11.029

Cited by 12 publications

(7 citation statements)

References 34 publications

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“…A similar result was observed for the postfunctionalization of polythiophene derivatives [25]. This study also suggested that the use of stronger acceptor molecules, such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its derivatives [26][27][28][29][30][31][32][33][34], is effective for the dramatic lowering of the LUMO levels or the enhancement of the n-type characteristics.…”

Section: Introductionsupporting

confidence: 76%

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Murata

Michinobu

2011

Polym. Bull.

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Electron-rich, side chain alkynes of an aromatic polyamine were functionalized by a [2?2] cycloaddition, followed by retro-cyclization with the electronaccepting 7,7,8,8-tetracyanoquinodimethane (TCNQ). 1 H NMR studies were used to optimize the reaction conditions. Mild heating to [50°C afforded the postfunctionalized aromatic polyamines with the desired acceptor amounts. The quantitative TCNQ addition was demonstrated by the MALDI-TOF mass spectrum and elemental analysis. Introduction of the cyano-based acceptor moieties into the polymer side chains resulted in unusually strong intermolecular interactions. In addition to the p-p interactions of the extended acceptor moieties, these intermolecular forces were supposed to improve the thermal stability of the aromatic polymers. Furthermore, the donor-acceptor chromophores formed by this postfunctionalization displayed low energy charge-transfer bands and redox activities in both the anodic and cathodic directions. The straightforward postfunctionalization technique using the alkyne-TCNQ addition is useful for the preparation of narrow band gap polymers in one step.

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Section: Introductionsupporting

confidence: 76%

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Murata

Michinobu

2011

Polym. Bull.

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“…The structure determination reveals that the C 6 quinoid group is attached to C(13), i.e., nearer to the electron-rich metal center, with the C(CN) 2 group being attached to C(14). This mode of addition was previously found in reactions of TCNQ with Ni(CCR)(PPh 3 )Cp, Ru(CCR)(dppe)Cp* (R = H, Ph), and Ru{CCCCCC[CCo 3 (μ-dppm)(CO) 7 ]}(dppe)Cp* . In all of these reactions, cycloaddition of TCNQ is stereospecific, the C(CN) 2 group residing further from the metal center; no evidence was found for the formation of any isomeric product resulting from the alternative mode of addition.…”

Section: Resultssupporting

confidence: 63%

“…The deep red-purple complexes obtained from trans -Pt(CCR) 2 (PR′ 3 ) 2 (R = H, Me, Et; R′ = Me, Et) and TCNQ were initially considered to be the CT adducts, but were later shown by an X-ray study to be the butadienyl-platinum(II) derivatives, trans -Pt(CCR){C[C 6 H 4 C(CN) 2 ]CRC(CN) 2 }(PR′ 3 ) 2 , formed by [2 + 2]-cycloaddition of TCNQ to one CC triple bond, followed by ring-opening of the resulting cyclobutenyls . Similar chemistry was described several years later for some arylalkynyl-nickel systems and for a mixed-metal Co 3 {C(CC) 3 }Ru complex. , …”

Section: Introductionmentioning

confidence: 64%

“…18 Similar chemistry was described several years later for some arylalkynyl-nickel systems and for a mixed-metal Co 3 {C(CC) 3 }Ru complex. 19,20 In a more detailed study, we have recently described reactions of TCNQ with alkynyl-iron or -ruthenium complexes (Scheme 2). 21 These follow pathways similar to those found for TCNE, although it has also been possible to isolate and structurally characterize examples of the radical ion pair G (formed by 1-e oxidation) and the zwitterionic intermediate H (assumed but not previously isolated during related studies with TCNE), as well as the spiro-cyclobutenyl I and the η 1 -and η 3 -butadienyls (J and K, respectively).…”

Section: ■ Introductionmentioning

confidence: 99%

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Reactions of 7,7,8,8-Tetracyanoquinodimethane with Poly-ynyl Ruthenium and Iron Complexes

et al. 2012

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The reaction of tetracyanoquinodimethane (TCNQ) with Ru(CCCCH)(dppe)Cp* (5) at the outer (from Ru) CC triple bond gives η 1 -(butadienyl)ethynyl Ru{CCC[CHC(CN) 2 ]C 6 H 4 C-(CN) 2 }(dppe)Cp (8), which reacts with a second equivalent of diynyl-Ru complex to give {Ru(dppe)Cp*}{CCC[C 6 H 4 C(CN) 2 ]CH CHC[C(CN) 2 ]CC}{Ru(dppe)Cp*} (9). The Ph-substituted complexes M{CCCCPh}(dppe)Cp* (M = Fe 6-Fe, Ru 6-Ru) and Ru{(CC) 3 Ph}(PPh 3 ) 2 Cp (7) react with TCNQ to give the η 1 11), respectively. Single-crystal X-ray diffraction molecular structure determinations for 8−11 have been carried out. In the Fe series, we suggest that the initial step of the mechanism involves electron transfer to form the [TCNQ] −• salt of the diynyl-iron cation, followed by C−C bond formation to give a zwitterionic intermediate. Isolated products can be rationalized by further reaction involving [2 + 2]-cycloaddition of one of the CC(CN) 2 groups of TCNQ to a CC triple bond of the metal poly-ynyl complex and a subsequent ring-opening reaction of the resulting (unobserved) cyclobutenyl intermediate. On the basis of X-ray diffraction data, redox potential determinations, and 57 Fe Mossbauer and UV−vis spectroscopies, the electronic structures of the new compounds contain significant contributions from polarized mesomers involving charge transfer from the electron-rich metal−ligand fragment to the cyanocarbon ligand via the conjugated unsaturated carbon linker.

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“…62 Since this initial report, several other examples of TCNQ-derived expanded TCBDs have been reported. [63][64][65][66][67][68] Importantly, the reaction is completely regioselective with respect to TCNQ, occurring exclusively at one exocyclic CQC double bond adjacent to the DCV moiety and not at the endocyclic double bonds. A similar regioselectivity was previously observed in the Diels-Alder reaction of TCNQ with in situ generated ortho-quinodimethane, reported by Martı´n and Hanack.…”

Section: Donor-substituted Expanded 7788-tetracyanoquinodimethanesmentioning

confidence: 99%

Non-planar push–pull chromophores

2010

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The development of a unique class of non-planar push-pull chromophores by means of [2 + 2] cycloaddition, followed by cycloreversion, of electron-deficient olefins, such as tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)-TCNQ), as well as dicyanovinyl (DCV) and tricyanovinyl (TCV) derivatives, to donor-substituted alkynes is explored in this feature article. This high-yielding, "click-chemistry"-type transformation with acetylenic dendrimers affords dendritic electron sinks capable of multiple electron uptake within a narrow potential range. An [AB]-type oligomer with a dendralene backbone was synthesised by a one-pot, multi-component cascade reaction of polyyne oligomers with TCNE and tetrathiafulvalene (TTF). In most cases, the resulting chromophores feature intense intramolecular charge-transfer bands extending far into the near infrared region and some of them display high third-order optical nonlinearities. Despite substitution with strong donors, the electron-withdrawing moieties in the new chromophores remain potent acceptors and a number of them display positive first reduction potentials (vs. the ferrocenium/ferrocene (Fc(+)/Fc) couple in CH(2)Cl(2)), which rival those of parent TCNE, TCNQ and F(4)-TCNQ. The non-planarity of the chromophores strongly enhances their physical properties when compared to planar push-pull analogues. They feature high solubility, thermal stability and sublimability, which enables formation of amorphous, high-optical-quality thin films by vapour phase deposition and makes them interesting as advanced functional materials for novel opto-electronic devices.

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The reactions of some σ-alkynylnickel complexes with 7,7,8,8-tetracyanoquinodimethane

Cited by 12 publications

References 34 publications

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Reactions of 7,7,8,8-Tetracyanoquinodimethane with Poly-ynyl Ruthenium and Iron Complexes

Non-planar push–pull chromophores

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