Journal
INORGANICA CHIMICA ACTA
Volume 367, Issue 1, Pages 73-84Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2010.12.008
Keywords
Diorganotin(IV); 4-Acyl-5-pyrazolones; NMR, Crystal structures; Solid state (119)Sn MAS NMR
Categories
Funding
- Universita degli Studi di Camerino
- Consiglio Nazionale delle Ricerche C.N.R.- Rome, Research Committee
- Vassar College
- EPSRC
- University of Warwick
- Advantage West Midlands (AWM)
- European Regional Development Fund (ERDF)
- Camille and Henry Dreyfus Foundation
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New (Q)(2)SnR(2) derivatives (HQ in general; in detail: HQ(CHPh2) = 4-diphenylacetyl-3-methyl-1-phenyl-5-pyrazolone; HQ(Bn) = 3-methyl-1-phenyl-4-phenylacetyl-5-pyrazolone; HQ(naph) = 3-methyl-4-naphthoyl-1-phenyl-5-pyrazolone; R = CH(3), C(2)H(5), C(6)H(11), n- and t-C(4)H(9), C(6)H(5),) have been synthesised and characterised by analytical and spectral techniques. Variable temperature NMR studies of (Q(CHPh2))(2)SnR(2) derivatives (R = CH(3) and C(2)H(5)) in chlorohydrocarbon solvents indicate a fluxional behaviour, with rapid interconversion between six- and five-coordinate species, the latter containing a bidentate acylpyrazolonate and a monodentate one. The X-ray crystal structures of the diorganotin(IV) derivatives (Q(CHPh2))(2)SnMe(2), (Q(CHPh2))(2)SnEt(2), (Q(Bn))(2)SnMe(2) and (Q(naph))(2)SnBu(2)(n), inclusive of a representative of each Q(x) family, show the metal centres in a skewed trans octahedral configuration. The 4-acyl moiety of the beta-diketonate donor exerts a steric effect which is correlated to structural behaviour in the solid and solution state. A solid state (119)Sn CPMAS NMR study of the (Q(Bn))(2)SnR(2) (R = CH(3), C(2)H(5), t-C(4)H(9) and C(6)H(5)) complexes shows a marked deshielding effect and upfield movement of the 119Sn isotropic chemical shift (delta(iso)) through this series. The (119)Sn chemical shift spans (Omega) are the largest reported for directly oxo-coordinated Sn(IV) systems, although the markedly reduced Omega value for the (Q(Bn))(2)SnPh(2) complex may be indicative of a cis octahedral coordination, in contrast to the trans octahedral coordination characterising the other complexes of this suite. (C) 2010 Elsevier B.V. All rights reserved.
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