1083165-58-5Relevant articles and documents
Synthesis and characterisation of mixed ligand Pt(ii) and Pt(iv) oxadiazoline complexes
Sarju, Julien,Arbour, Jannine,Sayer, James,Rohrmoser, Benjamin,Scherer, Wolfgang,Wagner, Gabriele
, p. 5302 - 5312 (2009/02/06)
The nitrile ligands in trans-[PtX2(PhCN)2] (X = Cl, Br, I) undergo sequential 1,3 dipolar cycloadditions with nitrones R 1R2C=N+(Me)-O- (R1 = H, R2 = Ph; R1 = CO2Et, R2 = CH 2CO2Et) to selectively form the Δ4-1,2,4- oxadiazoline complexes trans-[PtX2(PhCN) {N=C(Ph)-O-N(Me)-CR 1R2}] or trans-[PtX2{N=C(Ph)-O-N(Me)-CR 1R2}2] in high yields. The reactivity of the mixed ligand complexes trans-[PtX2(PhCN){N=C(Ph)-O-N(Me)-CR 1R2}] towards oxidation and ligand substitution was studied in more detail. Oxidation with Cl2 or Br2 provides the Pt(iv) species trans-[PtX2Y2(PhCN){N=C(Ph)-O-N(Me)- CH(Ph)}] (X, Y = Cl, Br). The mixed halide complex (X = Cl, Y = Br) undergoes halide scrambling in solution to form trans-[PtX(4-n)Y n(PhCN){N=C(Ph)-O-N(Me)-CH(Ph)}] as a statistical mixture. Ligand substitution in trans-[PtCl2(PhCN){N=C(Ph)-O-N(Me)-CR 1R2}] allows for selective replacement of the coordinated nitrile by nitrogen heterocycles such as pyridine, DMAP or 1-benzyl-2- methylimidazole to produce mixed ligand Pt(ii) complexes of the type trans- [PtX2(heterocycle){N=C(Ph)-O-N(Me)-CR1R2}]. All compounds were characterised by elemental analysis, mass spectrometry, IR and 1H, 13C and 195Pt NMR spectroscopy. Single-crystal X-ray structural analysis of (R,S)-trans-[PtBr 2{N=C(Ph)-O-N(Me)-CH(Ph)}2] and trans-[PtCl 2(C5H5N){N=C(Ph)-O-N(Me)-CH(Ph)}] confirms the molecular structure and the trans configuration of the heterocycles relative to each other. The Royal Society of Chemistry.
