Alkene oxidation by platinum (II) oxo/hydroxo complexes

The facile reaction between tetranuclear Pt-oxo complex [(COD)4Pt4([mu]2-O)2Cl2]2[BF4]2 (1) and norbornene (NB) yields the stable platinaoxetane [(COD)2Pt2(OC7H10)Cl][BF4] (2) in quantitative yield. A rapid reaction between NB and the novel (1,5-COD)Pt(II)-hydroxo complex [(COD)2Pt(OH)2]2+ (4) is observed and the protonated platinaoxetane [(COD)Pt(OH)C7H10)]+ (5) is formed in quantitative yield. Both Pt-hydroxo complex 4 and protonated platinaoxetane 5 are found to be important species in the formation of platinaoxetane 2. Mechanisms for formation of platinaoxetanes 2 and 5 are proposed. Pt-hydroxo complex 4 reacts readily with ethylene, propylene and 1-butene. All three reactions, resembling Wacker chemistry, yield alkene oxidation products: acetaldehyde, acetone and ethyl-­‐methyl ketone, respectively. Pt-ethyl alkyl complexes are yielded as the only Pt containing complexes. A proposed mechanism for these alkene oxidations is described. Pt-hydroxo complex 4 also reacts with cyclohexene. In this case the reaction takes an allylic C-H activation pathway to produce the cyclohexyl allyl complex [(COD)Pt(C6H9)]+ (55).

Name thesis:degree_name

Ph. D.

Level thesis:degree_level

Doctoral

Discipline thesis:degree_discipline

Chemistry (MU)

Grantor dc:publisher

University of Missouri--Columbia

Year dc:date.issued

2011

Author dc:creator

• Weliange, Nandita Malathi

Advisor dc:contributor.advisor

• Sharp, Paul Ray

• platinaoxetane
• quantitative yield
• alkene oxidation products

Statement dc:rights

• OpenAccess.

Language dc:language.iso

eng, English

DOI

https://doi.org/10.32469/10355/14503

OAI identifier oai:identifier

oai:mospace.umsystem.edu:10355/14503