Formation of double cubanes [Sn(7)(NR)(8)] in the reactions of pyridyl and pyrimidinyl amines with Sn(NMe(2))(2): a synthetic and theoretical study

David R Armstrong; Francesca Benevelli; Andrew D Bond; Neil Feeder; Eilis A Harron; Alexander D Hopkins; Mary McPartlin; David Moncrieff; David Sáez; Elsje A Quadrelli; Anthony D Woods; Dominic S Wright

doi:10.1021/ic011090r

Formation of double cubanes [Sn(7)(NR)(8)] in the reactions of pyridyl and pyrimidinyl amines with Sn(NMe(2))(2): a synthetic and theoretical study

Inorg Chem. 2002 Mar 25;41(6):1492-501. doi: 10.1021/ic011090r.

Authors

David R Armstrong¹, Francesca Benevelli, Andrew D Bond, Neil Feeder, Eilis A Harron, Alexander D Hopkins, Mary McPartlin, David Moncrieff, David Sáez, Elsje A Quadrelli, Anthony D Woods, Dominic S Wright

Affiliation

¹ Department of Pure and Applied Chemistry, University of Strathclyde, 195 Cathedral Street, Glasgow G1 1XL, UK.

PMID: 11896718
DOI: 10.1021/ic011090r

Abstract

In contrast to the reactions of Sn(NMe(2))(2) with unfunctionalized primary amines (RNH(2)), which yield the simple imido Sn(II) cubanes [SnNR](4), the reactions of 2-pyridyl or 2-pyrimidinyl amines give the mixed-oxidation-state Sn(II)/Sn(IV) double cubanes [Sn(7)(NR)(8)]. In addition to [Sn(7)[2-N(5-Mepy)](8)] x 2thf (1 x 2thf) (py = pyridine) and [Sn(7)[2-N(pm)](8)] x 0.33thf (2 x 0.33thf) (pm = pyrimidine), which were communicated previously, the syntheses and structures of the new complexes [Sn(7)[2-N(4-Mepm)](8)] x 2thf (3 x 2thf), [Sn(7)[2-N(4,6-Me(2)pm)](8)] x 4thf (4 x 4thf), [Sn(7)[2-N(4-Me-6-MeO-pm)](8)] (5), and [Sn(7)[2-N(4-MeO-6-MeO-pm)](8)] (6) are reported. Model DFT calculations on the reactions of Sn(NMe(2))(2) with 2-pmNH(2) or PhNH(2), producing the cubanes [Sn[2-N(pm)]](4) and [SnNPh](4) (respectively), and the corresponding double cubanes [Sn(7)[2-N(pm)](8)] and [Sn(7)(NPh)(8)], show that the presence of intramolecular Sn...N bonding which spans the cubane halves of the complexes is crucial to the formation of the double-cubane structure.