Antisymbiosis. Preferential coordination of anionic oxygen versus neutral sulfur donor atoms of methylsulfanyl- or methylsulfinyl-acetato, 2-benzoato and 2-phenolato to the cis-Pt(PPh3)2 and Pt(dppe) residues |
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| Authors: | Laura Battan Mario Manassero Alessandro Pasini Mirella Sansoni |
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| Affiliation: | a Dipartimento di Chimica Inorganica, Metallorganica e Analitica, via Venezian 21, 20133 Milano, Italy
b Dipartimento di Chimica Strutturale e Stereochimica Inorganica, via Venezian 21, 20133 Milano, Italy |
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| Abstract: | The interaction of an excess of the title ligands L− with the cis-Pt(phos)2 moieties gives compounds a-bcis-[Pt(L-O)2(phos)2] (a, phos = P(Ph)3; b, phos = 1/2 dppe), in which O- is preferred to S-coordination. Such preference is confirmed by the fact that the same products are obtained by reaction of excess of L− with the previously reported a-d complexes [Pt(L-O,S)(phos)2]+, (c, phos = PPh3, d, phos = 1/2 dppe), for which chelate ring opening occurs with rupture of Pt-S rather than Pt-O bonds. Compound a can be obtained also by oxidative addition of HL to [Pt(PPh3)3]. The Pt-O bonds in compounds a-d are stable towards substitution by Me2SO, pyridine and tetramethylthiourea. Substitution of L’s occurs with N,N′-diethyldithiocarbamate, which forms a very stable chelate with Pt(II). Thiourea and N,N′-dimethylthiourea also react, because they give rise to cyclometallated products [Pt(phos)2(NRC(S)NHR)]+ (R = H, CH3), with one ionised thioamido group, as revealed by an X-ray investigation of [Pt(PPh3)2(NHC(S)NH2)]+. The preference of O versus S coordination, as well as the stability of the Pt-O bonds, are discussed in terms of antisymbiosis. |
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| Keywords: | Antisymbiosis Platinum phosphine complexes Pt-O bonds |
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