Publication Type Journal Article
Title Microwave synthesis of bis(tetrazolato)-Pd-II 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 Pd-II Centre
Authors Jamal Lasri Maria Jose Fernandez Rodriguez M. Fátima C. Guedes da Silva P. Smolenski Maximilian N. Kopylovich J.J.R. Fraústo da Silva Armando J.L. Pombeiro
Groups CCC
Journal JOURNAL OF ORGANOMETALLIC CHEMISTRY
Year 2011
Month November
Volume 696
Number 22
Pages 3513-3520
Abstract [2 + 3] Cycloaddition reactions of the di(azido)-Pd-II complex trans-[Pd(N-3)(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(N-3)(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 Pd-II. The [2 + 3] cycloadditions of [Pd(N-3)(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 degrees 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, H-1, C-13\H-1\ and P-31\H-1\ 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. (C) 2011 Elsevier B. V. All rights reserved.
DOI http://dx.doi.org/10.1016/j.jorganchem.2011.07.047
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Publisher
Book Title
ISSN 0022-328X
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Bibtex ID ISI:000295717300009
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