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Berthon-Gelloz, Guillaume
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article
Expedient, direct synthesis of (L)Pt(0)(1,6-diene) complexes from H 2PtCl6
Abstract
<p>The one-pot synthesis of useful [Pt<sub>2</sub>(0)(η<sup>4</sup>-1,6- diene)<sub>3</sub>] complexes, directly from H<sub>2</sub>PtCl <sub>6</sub>·xH<sub>2</sub>O, has remained an unaddressed problem. We have found that the treatment of an i-PrOH solution of H<sub>2</sub>PtCl <sub>6</sub>-XH<sub>2</sub>O by (Me<sub>3</sub>SiO)<sub>2</sub>MeSi(CH=CH <sub>2</sub>), in the presence of allyl ether (AE), followed by reaction of the in situ generated Pt(O) species with IPr carbene (IPr =1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene) enables the isolation of (IPr)Pt(AE) (I) 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(O) fragments in catalysis.</p>