Tin(IV) Fluoride Complexes with Tertiary Phosphane Ligands – A Comparison of Hard and Soft Donor Ligands

The first phosphane complexes of the hard Lewis acid SnF 4 have been synthesised including trans ‐[SnF 4 (PR 3 ) 2 ] (R = Me or Cy) and cis ‐[SnF 4 (diphosphane)] [diphosphane = R 2 P(CH 2 ) 2 PR 2 , R = Me, Et, Ph or Cy; o ‐C 6 H 4 (PR 2 ) 2 , R = Me or Ph] and characterised by IR and multinuclear NMR ( 1 H, 19 F, 31 P, 119 Sn) spectroscopy. The crystal structures of trans ‐[SnF 4 (PCy 3 ) 2 ] and cis ‐[SnF 4 {Et 2 P(CH 2 ) 2 PEt 2 }] are reported. Tin(IV) fluoride complexes of 2,2′‐bipyridyl, 1,10‐phenanthroline, MeO(CH 2 ) 2 OMe, Me 2 N(CH 2 ) 2 NMe 2 , pyridine and THF have been characterised by multinuclear NMR spectroscopy, the structures of cis ‐[SnF 4 (L–L)] (L–L = 1,10‐phenanthroline and MeO(CH 2 ) 2 OMe) determined, and the properties were compared with those of the phosphane complexes. Complexes of o ‐C 6 H 4 (PMe 2 ) 2 , Et 2 P(CH 2 ) 2 PEt 2 , and MeC(CH 2 AsMe 2 ) 3 with SnCl 4 and SnBr 4 are also reported and the structures of cis ‐[SnCl 4 {Et 2 P(CH 2 ) 2 PEt 2 }] and cis ‐[SnBr 4 {κ 2 ‐MeC(CH 2 AsMe 2 ) 3 }] described. Attempts to prepare tertiary arsane complexes of SnF 4 have been unsuccessful. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)