Reversible CO2 activation by an N-phosphinoamidinato digermyne

This thesis describes the synthesis of the N-phosphinoamidinato digermynes [LG̈e–G̈eL] (E = Ge, L = tBu2PNC(Ph)NAr, 5: Ar = 2,6-iPr2C6H3, 6: Ar = Ph) by the reduction of the corresponding chlorogermylenes with KC8. Compounds 5 and 6 underwent reversible oxidative addition with CO2 in toluene at room...

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Bibliographic Details
Main Author: Quek, Shina
Other Authors: So Cheuk Wai
Format: Thesis-Master by Research
Language:English
Published: Nanyang Technological University 2022
Subjects:
Online Access:https://hdl.handle.net/10356/160026
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Institution: Nanyang Technological University
Language: English
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Summary:This thesis describes the synthesis of the N-phosphinoamidinato digermynes [LG̈e–G̈eL] (E = Ge, L = tBu2PNC(Ph)NAr, 5: Ar = 2,6-iPr2C6H3, 6: Ar = Ph) by the reduction of the corresponding chlorogermylenes with KC8. Compounds 5 and 6 underwent reversible oxidative addition with CO2 in toluene at room temperature to form [LG̈eOC(O)G̈eL] (9: Ar = 2,6-iPr2C6H3, 10: Ar = Ph). The reversibility was rationalized by NMR spectroscopy and DFT calculations. Compound 10 demonstrated the capability of executing sequential elementary organometallic processes with multiple substrates in its reaction with CO2 and phenylacetylene, as well as CO2 and hexafluorobenzene to form [LG̈eC(Ph)=C(Ph)G̈eL] (11), [LG̈eF] (12) and [LG̈eC6F5] (13), respectively.