MeNC Insertion into Pd–C6F5bonds: bis(µ-imidoyl-C,N)palladium complexes, a novel type of imidoyl co-ordination in palladium chemistry. Single-crystal X-ray structure of [Pd2{µ-C(C6F5)N(Me)}2Cl2(SC4H8)2]

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Abstract
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(C6F5)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 [LCl[graphic omitted]dClL]. {For L = CNMe the complex can also be obtained by heating trans-[Pd(C6F5)Cl(CNMe)2].} The polymer also reacts with Tl(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.

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