The chemistry of aryloxide and alkoxide tin(IV) compounds

Glen Douglas Smith, Purdue University

Abstract

Treatment of $\rm Sn(NMe\sb2)\sb4$ with 2,6-di-phenylphenol (HOAr) in hydrocarbon solvents leads to the initial formation of simple substitution products $\rm Sn(OAr)\sb2(NMe\sb2)\sb2$ and $\rm Sn(OAr)\sb3(NMe\sb2)$. Both of these compounds undergo rearrangement at room temperature to produce the corresponding bis- and mono-cyclometallated compounds $\rm Sn(OC\sb6H\sb3Ph$-$\rm C\sb6H\sb4)\sb2(NHMe\sb2)\sb2$ and $\rm Sn(OC\sb6H\sb3Ph$-$\rm C\sb6H\sb4)(OAr)\sb2(NHMe\sb2)$ in almost quantitative yields. Kinetic measurements show the formation of the six-membered metallacycles to be first-order while the results of substituent studies strongly implicate an E.A.S. pathway for the reaction. Facile five-membered metallacycle formation via aromatic CH bond activation of other alkoxide ligands by tin(IV) has also been demonstrated. Hence the alkoxide compounds $\rm Sn(OCPh\sb3)\sb2(NMe\sb2)\sb2$ and $\rm Sn(OCMe\sb2Ph)\sb4$ upon heating form the cyclometallated derivatives $\rm Sn(OCPh\sb2$-$\rm C\sb6H\sb4)\sb2(NHMe\sb2)\sb2$ and $\rm \lbrack Sn(OCMe\sb2$-$\rm C\sb6H\sb4)\sb2\rbrack \sb2$ respectively.

Degree

Ph.D.

Advisors

Rothwell, Purdue University.

Subject Area

Chemistry

COinS