Synthesis and reactivity of platinum vinylcarbene complexes prepared from activation of propargyl alcohols

Publication date: Available online 23 October 2018Source: Journal of Organometallic ChemistryAuthor(s): Wenqing Ruan, Chuan Shi, Herman H.Y. Sung, Ian D. Williams, Guochen JiaAbstractPlatinum vinylcarbene complexes are potentially useful for organometallic synthesis and catalysis, but have been rarely studied. This work reports a convenient route to make platinum vinylcarbene complexes. Treatment of [PtCl2(PPh3)]2 with propargyl alcohols HC≡CC(OH)RR’ (RR’ = Ph2, cyclo-C6H10(OH), (iPr)(C≡CTMS) and (H)(Ph)) in the presence of EtOH produced the vinylcarbene complexes trans-PtCl2{ = C(OEt)-CH=CRR’}(PPh3). Under similar condition, [PtCl2(PPh3)]2 reacted with HC≡CC(OH)Me2 to give cis-PtCl2{ = C(OEt)-CH=CMe2}(PPh3). Complex trans-PtCl2{ = C(OEt)-CH=CPh2}(PPh3) readily undergo a metathesis reaction with NaI to give trans-PtI2{ = C(OEt)-CH=CPh2}(PPh3) which can isomerize to cis-PtI2{ = C(OEt)-CH=CPh2}(PPh3). Complex trans-PtCl2{ = C(OEt)-CH=CPh2}(PPh3) reacted with PPh3 to give EtCl and the acyl complex trans-PtCl{C(O)CH=CPh2}(PPh3)2, which can undergo a decarbonylation reaction to give PtCl(CH=CPh2)(PPh3)2.Graphical abstractA convenient route to make platinum vinylcarbene complexes is described. Treatment of [PtCl2(PPh3)]2 with propargyl alcohols HC≡CC(OH)RR’ (RR’ = Ph2, cyclo-C6H10(OH), (iPr)(C≡CTMS) and (H)(Ph)) in the presence of EtOH produced the vinylcarbene complexes trans-PtCl2{=C(OEt)-CH=CRR’}(PPh3).

Source: Journal of Organometallic Chemistry - October 24, 2018 Category: Chemistry Source Type: research