Cycloneophylplatinum Chemistry: A New Route to Platinum(II) Complexes and the Mechanism and Selectivity of Protonolysis of Platinum–Carbon Bonds
Autor: | Richard J. Puddephatt, Mahmood Azizpoor Fard, Ava Behnia |
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Rok vydání: | 2018 |
Předmět: |
Denticity
010405 organic chemistry Organic Chemistry chemistry.chemical_element 010402 general chemistry Cleavage (embryo) 01 natural sciences Medicinal chemistry Chloride 0104 chemical sciences Inorganic Chemistry chemistry medicine Protonolysis Physical and Theoretical Chemistry Selectivity Platinum Carbon Isomerization medicine.drug |
Zdroj: | Organometallics. 37:3368-3377 |
ISSN: | 1520-6041 0276-7333 |
DOI: | 10.1021/acs.organomet.8b00650 |
Popis: | A new route to cycloneophylplatinum(II) complexes is reported and the selectivity of protonolysis of the platinum–aryl and −alkyl bonds has been determined. Reaction of [PtCl2(SMe2)2] with neophylmagnesium chloride gives the binuclear cycloneophylplatinum(II) complex [Pt2(CH2CMe2C6H4)2(μ-SMe2)2], 1, which is shown to exist as a mixture of syn and anti isomers. Complex 1 reacts reversibly with SMe2 to give [Pt(CH2CMe2C6H4)(SMe2)2], 2, and irreversibly with bidentate ligands NN = 3,4,7,8-tetramethyl-1,10-phenanthroline (phen*) or 4,4′-di-t-butyl-2,2’bipyridine (bubipy) to give the corresponding complexes [Pt(CH2CMe2C6H4)(phen*)], 3, and [Pt(CH2CMe2C6H4)(bubipy)], 4, respectively. Complex 2 reacts with HCl initially by cleavage of the aryl–platinum bond to give mostly trans-[PtCl(CH2CMe2Ph)(SMe2)2], which then rearranges to an equilibrium mixture with trans-[PtCl(C6H4-2-t-Bu)(SMe2)2], while 3 and 4 react to give [PtCl(CH2CMe2Ph)(phen*)] and [PtCl(CH2CMe2Ph)(bubipy)], which do not undergo the isomerization re... |
Databáze: | OpenAIRE |
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