The Reactivity of Ditetrelenes Towards Organophosphorus Oxides

The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group oxide that can be activated by ditetrelenes 4 and 5 in addition to nitro and sulfonyl containing compounds, CO and CO2. The mechanism for the reaction of diorganophosphorus oxides and phosphites with ditetrelenes 4 and 5 was investigated through deuterium labelling studies and KIE experiments. The mechanism for the formation of disilyl and digermyl phosphinites and phosphites was determined to proceed through a nucleophilic addition. An exchange phenomenon between the OP(pentyl)2 moiety of 32 and an OPPh2 group from diphenylphosphine oxide was discovered and insights into the mechanism of this exchange were obtained.

Name thesis:degree_name

M Sc

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

The University of Western Ontario

Year dc:date.issued

2019

Author dc:creator

• Belcina, Maissa

Advisor dc:contributor.advisor

• Baines, Kim M.

• Group 14
• silicon
• germanium
• disilene
• digermene
• organophosphorus oxides

Language dc:language.iso

en_ca

Handle dc:identifier.uri

https://hdl.handle.net/20.500.14721/29514

OAI identifier oai:identifier

oai:uwo.scholaris.ca:20.500.14721/29514