کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1322239 | 977189 | 2011 | 8 صفحه PDF | دانلود رایگان |

[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.
[2 + 3] Cycloadditions of [Pd(N3)2(L)2] (L = PPh3, PTA) with organonitriles give bis(tetrazolato) complexes. Reaction of trans-[Pd(N3)2(PPh3)2] with propionitrile also affords an unexpected mixed cyano-tetrazolato complex and 5-ethyl-1H-tetrazole, via an unusual oxidative addition of nitrile to PdII.Figure optionsDownload as PowerPoint slideHighlights
► Di(azido) compounds as starting materials for bis(5-substituted tetrazolato)-PdII complexes.
► The first example of C–CN bond cleavage of propionitrile by a PdII centre.
► Metal-mediated synthesis of tetrazole derivative.
Journal: Journal of Organometallic Chemistry - Volume 696, Issue 22, 1 November 2011, Pages 3513–3520