Novel bis(β-diketonato)diorganotin(IV) derivatives containing bulky 4-acyl-5-pyrazolonato ligands : Influence of the steric hindrance of the acyl moiety on the solid state structures of tin complexes and their behaviour in solution
Caruso, F. (Francesco), Di Nicola, Corrado, Hanna, John V., Marchetti, F. (Fabio), Pettinari, Claudio, Pettinari, Riccardo, Rossi, Miriam, Rees, Gregory J., Skelton, Brian W. and White, Allan H.. (2011) Novel bis(β-diketonato)diorganotin(IV) derivatives containing bulky 4-acyl-5-pyrazolonato ligands : Influence of the steric hindrance of the acyl moiety on the solid state structures of tin complexes and their behaviour in solution. Inorganica Chimica Acta, Vol.367 (No.1). pp. 73-84. ISSN 00201693Full text not available from this repository.
Official URL: http://dx.doi.org/10.1016/j.ica.2010.12.008
New (Q)2SnR2 derivatives (HQ in general; in detail: HQCHPh2 = 4-diphenylacetyl-3-methyl-1-phenyl-5-pyrazolone; HQBn = 3-methyl-1-phenyl-4-phenylacetyl-5-pyrazolone; HQnaph = 3-methyl-4-naphthoyl-1-phenyl-5-pyrazolone; R = CH3, C2H5, C6H11, n- and t-C4H9, C6H5,) have been synthesised and characterised by analytical and spectral techniques. Variable temperature NMR studies of (QCHPh2)2SnR2 derivatives (R = CH3 and C2H5) 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 (QCHPh2)2SnMe2, (QCHPh2)2SnEt2, (QBn)2SnMe2 and , inclusive of a representative of each Qx family, show the metal centres in a skewed trans octahedral configuration. The 4-acyl moiety of the β-diketonate donor exerts a steric effect which is correlated to structural behaviour in the solid and solution state. A solid state 119Sn CPMAS NMR study of the (QBn)2SnR2 (R = CH3, C2H5, t-C4H9 and C6H5) complexes shows a marked deshielding effect and upfield movement of the 119Sn isotropic chemical shift (δiso) through this series. The 119Sn chemical shift spans (Ω) are the largest reported for directly oxo-coordinated Sn(IV) systems, although the markedly reduced Ω value for the (QBn)2SnPh2 complex may be indicative of a cis octahedral coordination, in contrast to the trans octahedral coordination characterising the other complexes of this suite.
|Item Type:||Journal Article|
|Subjects:||Q Science > QC Physics
Q Science > QD Chemistry
|Divisions:||Faculty of Science > Physics|
|Library of Congress Subject Headings (LCSH):||Crystallography, Nuclear magnetic resonance, Pyrazolones, Solid state physics|
|Journal or Publication Title:||Inorganica Chimica Acta|
|Official Date:||28 February 2011|
|Page Range:||pp. 73-84|
|Access rights to Published version:||Restricted or Subscription Access|
|Funder:||Università di Camerino, Consiglio nazionale delle ricerche (Italy) (CNR) , Vassar College , Engineering and Physical Sciences Research Council (EPSRC), University of Warwick , Advantage West Midlands (AWM) , European Regional Development Fund (ERDF) , Camille and Henry Dreyfus Foundation|
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