Reactive Intermediates on Metal Surfaces: A Ketene Monolayer on Single Crystal Platinum Generated by Photolysis of Pyridyl α-Diazoketones

✍ Scribed by Jason L. Pitters; Keith Griffiths; Milan Kovar; Peter R. Norton; Mark S. Workentin

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 151 KB
• Volume: 39
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/1521-3773(20000616)39:12<2144::aid-anie2144>3.0.co;2-v

✦ Synopsis

There is considerable current interest in understanding the chemistry of organic molecules as monolayers (saturated layer) on metal surfaces. Much of the effort in this regard has focused on long-chain alkyl thiols or disulfides on gold with additional equivalent of MMA binds to the nickel center, possibly in place of the carbonyl group (Scheme 1). To account for the catalytic dependence of the reaction on [Ni(acac) 2 ] and the fact that the polymerization is centered at the Al(tBu 4 salen) component, transfer of the enolate from nickel to aluminum with concomitant transfer of the methyl group from aluminum to nickel is proposed (Scheme 1). This generates the active aluminum enolate species for polymerization and reforms the ª[Ni(acac)Me]º catalyst. In a separate study we have successfully synthesized the aluminum enolate species, [Al(tBu 4 salen){OC(OtBu)CMe 2 }], and shown that this is an efficient initiator for MMA polymerization. These results will be reported in due course.