Co-ordination chemistry of higher oxidation states. Part 4. Palladium(IV) complexes of nitrogen, phosphorus, and arsenic donor ligands. Crystal and molecular structures of [Pd(bipy)Cl4] and [Pd{o-C6H4(AsMe2)2}2Cl2][ClO4]2
- 1 January 1983
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 133-141
- https://doi.org/10.1039/dt9830000133
Abstract
Octahedral palladium(IV) complexes [Pd(L–L)Cl4][L–L = Me2NCH2CH2NMe2, 2,2′-bipyridyl (bipy), 1,10-phenanthroline (phen), Ph2PCH2CH2PPh2, Me2PCH2CH2PMe2, Ph2AsCH2CH2AsPh2, o-C6H4(AsMe2)2, and Me2As(CH2)3AsMe2] have been prepared by chlorine oxidation of [Pd(L–L)Cl2]. The corresponding [Pd(L–L)Br4][L–L = Me2PCH2CH2PMe2, o-C6H4(AsMe2)2, and Me2As(CH2)3AsMe2] have been obtained, but the [Pd(L–L)Br2](L–L = N-donors above, Ph2PCH2CH2PPh2 and Ph2AsCH2CH2AsPh2) were not oxidised by bromine. The complexes [Pd(L–L)X4](X = Cl or Br) reductively eliminate X2 on gentle heating. Chlorine oxidation of Pd(L–L)2Cl2 gave Pd(L–L)2Cl4 for L–L = Me2PCH2CH2PMe2 and o-C6H4(PMe2)2, but gave [Pd(L–L)Cl4] for L–L = Ph2PCH2CH2PPh2, Ph2AsCH2CH2AsPh2, and o-C6H4(AsMe2)2. The complexes trans-[Pd(L–L)2X2][ClO4]2[X = Cl or Br; L–L = Me2PCH2CH2PMe2, o-C6H4(PMe2)2, o-C6H4(AsMe2)2, or o-C6H4(PMe2)(AsMe2)] were obtained by HNO3–HX oxidation of Pd(L–L)2X2 followed by addition of HClO4. Infrared, electronic, and 1H n.m.r. spectra are reported for the complexes. Attempts to prepare PdtIV complexes with multidentate phosphines and arsines are described. The structures of the title compounds have been established by single-crystal X-ray studies. The complex [Pd(bipy)Cl4] is monoclinic, space group Pn, a= 12.241(5), b= 6.720(2), c= 8.120(9)Å, β= 104.37(5)°, and Z= 2. 1 383 Observed reflections [σ(F)⩽ 2F] refined R to 0.023. The crystal contains discrete octahedral molecules [Pd–Cl 2.289(1)–2.310(1), Pd–N 2.037(4), 2.044(4)Å]. The complex [Pd{o-C6H4(AsMe2)2}2Cl2][ClO4]2 is triclinic, space group P, a= 7.903(3), b= 10.670(3), c= 10.141(2)Å, α= 110.50(2), β= 91.75(3), γ= 107.31(3)°, and Z= 1. 1 680 Observed reflections [σ(F)⩽ 3F] refined R to 0.039. The crystal contains trans octahedral cations [Pd–Cl 2.302(2), Pd–As 2.452(1), 2.455(1)] and perchlorate ions [CI–O 1.42(1)Å].Keywords
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