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Microwave synthesis of bis(tetrazolato)-PdII complexes with PPh3 and water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA). The first example of C-CN bond cleavage of propionitrile by a PdII centre.

Autorzy

J. Lasri

M. J. Fernández Rodríguez

Silva M. Fátima. C. Guedes da

Piotr Smoleński

Maximilian N. Kopylovich

J. J. R. Fraústo da Silva

Armando J. L. Pombeiro

Rok wydania

2011

Czasopismo

Journal of Organometallic Chemistry

Numer woluminu

696

Strony

3513-3520

DOI

10.1016/j.jorganchem.2011.07.047

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

[2 + 3] Cycloaddition reactions of the di(azido)-PdII complex trans-[Pd(N3)2(PPh3)2] (1) with an organonitrile RCN (2), under heating for 12 h, give the bis(tetrazolato) complexes trans-[Pd(N4CR)2(PPh3)2] (3) [R = Me (3a), Ph (3b), 4-ClC6H4 (3c), 4-FC6H4 (3d), 2-NC5H4 (3e), 3-NC5H4 (3f), 4-NC5H4 (3g)]. The reaction of trans-[Pd(N3)2(PPh3)2] (1) with propionitrile (2h) also affords, apart from trans-[Pd(N4CEt)2(PPh3)2] (3h), the unexpected mixed cyano-tetrazolato complex trans-[Pd(CN)(N4CEt)(PPh3)2] (3h′) which is derived from the reaction of the bis(tetrazolato) 3h with propionitrile, with concomitant formation of 5-ethyl-1H-tetrazole, via a suggested unusual oxidative addition of the nitrile to PdII. The [2 + 3] cycloadditions of [Pd(N3)2(PTA)2] (4) (PTA = 1,3,5-triaza-7-phosphaadamantane) with RCN (2), under heating for 12 h, give the bis(tetrazolato) complexes trans-[Pd(N4CR)2(PTA)2] (5) [R = Ph (5a), 2-NC5H4 (5b), 3-NC5H4 (5c), 4-NC5H4 (5d)]. All these reactions are greatly accelerated by microwave irradiation (1 h, 125 °C, 300 W). Taking advantage of the hydro-solubility of PTA, a simple liberation of 5-phenyl-1H-tetrazole from the coordination sphere of trans-[Pd(N4CPh)2(PTA)2] (5a) was achieved. The complexes were characterized by IR, 1H, 13C{1H} and 31P{1H} NMR spectroscopies, ESI+-MS, elemental analyses and, for 3b, also by X-ray structure analysis. Weak agostic interactions between the CH groups of the triphenylphosphines and the palladium(II) centre were found.

Słowa kluczowe

atom, Ion, 5-Triaza-7-phosphaadamantane (PTA), Azides, Nitriles, [2 + 3] Cycloadditions, Tetrazoles, Microwaves

Adres publiczny

https://doi.org/10.1016/j.jorganchem.2011.07.047

Strona internetowa wydawcy

http://www.elsevier.com

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