Expedient, Direct Synthesis of (L)Pt(0)(1,6-diene) Complexes from H2PtCl6

• Published in: Organometallics Vol. 26; no. 23; pp. 5731 - 5734
• Main Authors: Berthon-Gelloz, Guillaume, Schumers, Jean-Marc, Lucaccioni, Fabio, Tinant, Bernard, Wouters, Johan, Markó, István E
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 05.11.2007; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; PALLADIUM; CATALYSIS; N-HETEROCYCLIC CARBENE; HYDROSILYLATION; CHEMISTRY; CONVENIENT; CRYSTAL; ALKYNES; PLATINUM COMPLEXES; PHOSPHINE) COMPLEXES
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om7007088

The one-pot synthesis of useful [Pt2(0)(η4-1,6-diene)3] complexes, directly from H2PtCl6·xH2O, has remained an unaddressed problem. We have found that the treatment of an i-PrOH solution of H2PtCl6·xH2O by (Me3SiO)2MeSi(CHCH2), in the presence of allyl ether (AE), followed by reaction of the in situ generated Pt(0) species with IPr carbene (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) enables the isolation of (IPr)Pt(AE) (1) in 50−70% yield. The scope of this method has been extended to other (L)Pt(1,6-diene) complexes (L = 1,3-dicyclohexylimidazol-2-ylidene, triphenylphoshine; 1,6-diene = diethyl 2,2-diallylmalonate (DAM)), and the molecular structure of the (IPr)Pt(DAM) (4) complex has been unequivocally determined by a single-crystal X-ray diffraction analysis. These results are significant for the formation of active L−Pt(0) fragments in catalysis.