The charge-transfer interaction of 7,7,8,8-tetracyanoquinodimethane with trans-bis(trialkylphosphine)-dialkynylplatinum(II) and related complexes

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Abstract

7,7,8,8-Tetracyanoquinodimethane★★ (TCNQ) showed charge-transfer interaction with trans-bis(trialkylphosphine)dialkynylplatinum(II), trans-[R′3P)2Pt-(CCR)2], (R′ = Me, Et, Pr, Bu, and R = H, Me, CH2CH, CH3CC or Ph), and their palladium(II) and nickel(II) derivatives. The following 11 adducts were isolated as stable purple-black crystals:

These adducts showed a characteristic absorption band in the visible region (λmax; 506–555 nm in CH2Cl2).

From the study of their formation constants and consideration of the molecular geometry of component molecules, it was deduced that electron was donated from the alkynyl groups to TCNQ. This characteristic property of the alkynyl group which coordinates to transition-metal atom is regarded as the consequence of the back-donation of electrons from the central metal which increases the electron density on the alkynyl groups and enhances their donor properties.

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    Citation Excerpt :

    The η3-allyl Ru{η3-CPhCHCCPh(CCPh)}(PPh3)Cp* 15 probably reacts with TCNE by opening of the allyl chelate, coordination of TCNE and intramolecular cycloaddition of TCNE to the alkynyl group to give Ru{C(CHCHPh)CPhC[CPhC(CN)2]C(CN)(η2-CN)}(PPh3)Cp* 16 (Scheme 5) [18]. The usual η1-tetracyano-dienyl complex, RuCl{C[C(CN)2]CPhC(CN)2}(CNxy)(η6-C6Me6) was obtained either directly, from reactions of TCNE with RuCl(CCPh)(CNxy)(η6-C6Me6), or with RuCl(CCPh)(PPh3)(η6-C6Me6) by loss of PPh3 to give the η3-dienyl, followed by addition of xyNC [19]. In the reaction between TCNE and Ru(CCH)(dppe)Cp*, nucleophilic displacement of a CN group from the cyano-alkene gives the tricyanovinylethynyl complex Ru{CCC(CN)C(CN)2}(dppe)Cp* 17a with loss of HCN (Scheme 6) [12].

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Chemical Abstracts name: 3,6-bis(dicyanomethylene)-1,4-cyclohexadiene.

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