SOME UNUSUAL METHYLATIONS AND ARYLATIONS OF PLATINUM(II) CHLORIDES BY ORGANOTIN COMPOUNDS - C-13 NMR-SPECTRA OF BIS-ARYL(ETA-CYCLOOCTA-1,5-DIENE)PLATINUM(II) COMPLEXES

Treatment of [Pt(COD)Cl2] with SnMe4 in Cl2CHCHCl2 at 100°C has been shown to give [Pt(COD)(Me)Cl] in 59% yield, while use of Me2SO as solvent gives [PtMe2(Me2SO)2], and hence [PtMe2(PPh3)2] in 50% yield. Interaction of [Pt(COD)Cl2] with Sn(C6H4SMe-p)Me3 gives the polymeric species [Pt(C6H4SMe-p)2]n. Treatment of [Pt(COD)Cl2] with 1-trimethylstannyl- or bis(1,1′-trimethylstannyl)-ferrocene gives [Pt(COD)(C5H4FeC5H5)Cl] or the ferrocenyl-bridged[Pt(COD)Cl(C5H4FeC5H4)Cl(COD)Pt]. Treatment of trans-[Pt2Cl4(PEt3)2] with Sn(C6H4Me-p)Me3 readily brings about replacement of the terminal chloride ligands to give [Pt2(C6H4Me-p)2Cl2(PEt3)2]. The 13C NMR spectra of various [Pt(COD)(C6H4X)2] complexes are reported, and also values of the longest wavelength maximum, λmax, in the visible spectrum of [Pt(C6H4X)2(BIPY)]. The values of the 13C chemical shifts for the olefinic protons of the COD complexes given an excellent linear correlation with σ° values of the X groups, and with the values of λmax for the BIPY complexes. © 1979.