MeNC insertion into Pd-C6 F5 bonds:bis(mu-imidoyl C,N) Palladium complexes, a novel type of imidoyl coordination in palladium chemistry. Single crystal X-ray of [Pd2{mu-C(C6F5)=NMe}2Cl2(SC4H8)2]
- Usón, R. 2
- Forniés, J. 2
- Espinet, P. 2
- Lalinde, E. 2
- Jones, P.G. 1
- Sheldrick, G.M. 1
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1
University of Göttingen
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2
Universidad de Zaragoza
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ISSN: 0300-9246
Año de publicación: 1982
Volumen: 12
Páginas: 2389-2395
Tipo: Artículo
Otras publicaciones en: Journal of the Chemical Society-Dalton Transactions
Resumen
The complex cis- or trans-[Pd(C6F5)2(CNMe)2] reacts with PdCl2 or [PdCl2(NCPh)2] to give [Pd2(μ-Cl)2(C6F5)2 (CNMe)2] which in turn undergoes MeNC insertion to give cis-[{Pd2(μ-Cl)2[μ-C(C6F 5)=N(Me)]2}n]. The latter undergoes cleavage of the chloro-bridges by neutral ligands [L = CNMe, NMe3, py, 4Me-py, 4But-py (py = pyridine), PPh3, and SC4H8] affording dimeric complexes [LClPd{C(C6F5)=N (Me)}{(Me)N=C(C6F5)}PdClL]. {For L = CNMe the complex can also be obtained by heating trans-[Pd(C6F5)Cl(CNMe)2].} The polymer also reacts with TI(acac) (acac = acetylacetonate) or Ag(O2CMe) affording the corresponding imidoyl-bridged dimers. The 1H n.m.r. spectra show a mixture of two isomers for L = py, 4Me-py, and 4But-py; the four 19F n.m.r. spectra recorded reveal restricted rotation for the C6F5 group. The bridging location of the imidoyl groups has been ascertained by a single-crystal X-ray structure determination of the complex with L = SC4H8 (tetrahydrothiophen), which crystallizes in the monoclinic space group P21/c, with unit-cell dimensions a = 9.304(2), b = 9.563(2), c = 34.979(5) Å, β = 95.76(2)°, and Z = 4. The structure was solved by the heavy-atom method and refined to R = 0.040 for 3 978 observed reflections.