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Insertion of Substituted Alkynes into the Pd−C Bond of Methyl and Vinyl Palladium(II) Complexes Bearing Pyridylthioethers as Ancillary Ligands. The Influence of Ligand Substituents at Pyridine and Sulfur on the Rate of Insertion

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Dipartimento di Chimica, Università Ca’ Foscari, Calle Larga S. Marta 2137, 30123 Venezia, Italy, and Dipartimento di Scienze Farmaceutiche, Università di Padova, Via F. Marzolo 5, 35131 Padova, Italy
Cite this: Organometallics 2005, 24, 13, 3297–3308
Publication Date (Web):May 20, 2005
https://doi.org/10.1021/om058005y
Copyright © 2005 American Chemical Society

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    Abstract

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    The palladium(II) chloro methyl complexes bearing the bidentate 6-R-C5H3N-2-CH2SR‘ (RN-SR‘; R = H, Me, Cl; R‘ = Me, t-Bu, Ph) and the potentially terdentate 2,6-(CH2SR‘)2-C5H3N (S-N-S(R‘); R‘ = Me, t-Bu, Ph) pyridylthioethers as ancillary ligands were synthesized, characterized, and reacted with substituted alkynes ZC⋮CZ (Z = COOMe, Z‘ = COOt-Bu, Z‘ ‘ = COOEt). The reactions were followed under second-order conditions by 1H NMR technique, and the reaction rates were determined. The corresponding vinyl derivatives were synthesized, and in the case of the complexes [PdCl(ZCCZMe)(MeN-SPh)] and [PdCl(ZCCZMe)(C1N-St-Bu)] (Z = COOMe) reaction rates for alkyne insertion yielding the corresponding butadienyl complexes were also determined. The rate of insertion of the second alkyne on the vinyl complex is more than 3 orders of magnitude lower than the first insertion rate in both the studied complexes, thereby allowing easy separation between vinyl and butadienyl derivatives and an easy preparation of mixed butadienyl esters. Furthermore, the reaction rates are strongly dependent on the steric and electronic features of the ancillary ligands. In particular, the distortion of the complex main coordination plane, induced by the substituent in position 6 of the pyridine ring, was found to significantly influence the substrate reactivity. The structures of the mono-inserted vinyl [PdCl(ZCCZMe)(MeN-St-Bu)] (1) and the bis-inserted butadienyl [PdCl((ZCCZ)2Me)(MeN-St-Bu)] (2) complexes were determined by X-ray diffraction, and the persistence of a structural distortion of the complex skeleton was observed. Moreover, the distortion may be related to facile ancillary ligand displacement, a feature that can be exploited for the synthesis of substrates that would not be easily obtained otherwise.

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    *

     To whom correspondence should be addressed. E-mail:  cano@ unive.it.

     Università Ca’ Foscari.

     Università di Padova.

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    Text giving details of the X-ray crystal structure studies and table of crystal structure determination data, atomic coordinates, anisotropic thermal parameters, bond lengths and angles (CIF files) and NOESY graphic output are available free of charge via the Internet at http://pubs.acs.org.

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