The first phosphane complexes of the hard Lewis acid SnF4 have been synthesised including trans‐[SnF4(PR3)2] (R = Me or Cy) and cis‐[SnF4(diphosphane)] [diphosphane = R2P(CH2)2PR2, R = Me, Et, Ph or Cy; o‐C6H4(PR2)2, R = Me or Ph] and characterised by IR and multinuclear NMR (1H, 19F, 31P, 119Sn) spectroscopy. The crystal structures of trans‐[SnF4(PCy3)2] and cis‐[SnF4{Et2P(CH2)2PEt2}] are reported. Tin(IV) fluoride complexes of 2,2′‐bipyridyl, 1,10‐phenanthroline, MeO(CH2)2OMe, Me2N(CH2)2NMe2, pyridine and THF have been characterised by multinuclear NMR spectroscopy, the structures of cis‐[SnF4(L–L)] (L–L = 1,10‐phenanthroline and MeO(CH2)2OMe) determined, and the properties were compared with those of the phosphane complexes. Complexes of o‐C6H4(PMe2)2, Et2P(CH2)2PEt2, and MeC(CH2AsMe2)3 with SnCl4 and SnBr4 are also reported and the structures of cis‐[SnCl4{Et2P(CH2)2PEt2}] and cis‐[SnBr4{κ2‐MeC(CH2AsMe2)3}] described. Attempts to prepare tertiary arsane complexes of SnF4 have been unsuccessful. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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The first series of phosphane oxide complexes of germanium(IV) halides have been prepared, including trans‐[GeF4(R3PO)2] (R = Me, Et or Ph), trans‐[GeCl4(Et3PO)2], fac‐[GeCl3(Me3PO)3]2[GeCl6] and cis‐[GeX2(Me3PO)4]X2 (X = Cl or Br) and characterised by IR and multinuclear NMR (1H, 19F{1H} and 31P{1H}) spectroscopy. Crystal structures of all the above (except trans‐[GeCl4(Et3PO)2]) are described. Remarkably, under mild conditions Me3PO displaces halide ligands from GeX4 (X = Cl, Br) to form the cationic species above. Ph3AsO forms trans‐[GeF4(Ph3AsO)2], but reaction of Ph3AsO or Me3AsO with GeCl4 leads to the corresponding R3AsCl2. The complexes [GeF4(MeCN)2], [GeF4(thf)2] and [GeF4(MeOCH2CH2OMe)] are also described and the relative Lewis acidities of GeX4 established. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The six‐coordinate adducts cis‐[GeX4(L–L)] (L–L = 2,2′‐bipyridyl, 1,10‐phenanthroline, or Me2NCH2CH2NMe2, X = F, Cl or Br) have been synthesised and characterised by IR and VT 1H and 19F{1H} NMR spectroscopy. X‐ray crystal structures reveal distorted octahedral geometries and the trends in d(Ge–N) with halide are interpreted in terms of varying Lewis acidity within the series. The trans‐[GeX4(py)2] were similarly characterised. In contrast, GeI4 does not form similar adducts, although it appears to co‐crystallise with some of the ligands, and the structure of GeI4·(1,10‐phenH)3·I3 which contains phenanthrolinium cations, iodide anions and tetrahedral GeI4 molecules is reported. Multidentate nitrogen donor ligands including cyclam (1,4,8,11‐tetraazacyclotetradecane) and Me4‐cyclam (1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane) react with [GeF4(MeCN)2] to form insoluble compounds [{GeF4}2(macrocycle)] (F4N2 donor sets). In contrast, Me3[9]aneN3 (1,4,7‐trimethyl‐1,4,7‐triazacyclononane) forms the cation [GeF3{Me3[9]aneN3}]+ with a facial geometry (N3F3 donor set) which is the first example of displacement of fluoride from GeF4 by a neutral ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Abstract[VOF3(MeCN)], obtained by dissolving VOF3 in dry acetonitrile, is a useful synthon for the preparation of complexes of the oxide‐fluoride, and the reaction with 2,2′‐bipyridyl, 1,10‐phenanthroline, Me2N(CH2)2NMe2 and Ph2P(O)CH2P(O)Ph2 (L–L), or Ph3PO, Me3PO, Ph3AsO, pyridine and pyridine N‐oxide (L), produces the complexes [VOF3(L–L)] or [VOF3(L)2] respectively. These were characterised by microanalysis, IR, UV/Vis and multinuclear NMR [51V, 19F{1H}, 31P{1H}, 1H] spectroscopy, the data showing them to besix‐coordinate with trans F–V–F units and the neutralligands trans to O and F, respectively. X‐ray crystal structures of [VOF3(1,10‐phenanthroline)], [VOF3(Ph3PO)2] and [VOF3(pyNO)2] confirm the geometry, although the first two exhibit O/F disorder trans to the neutral ligand. Unstable complexes with ether and thioether ligands including [VOF3{MeO(CH2)2OMe}], [VOF3{MeS(CH2)2SMe}] and [VOF3(15‐crown‐5)] are also described; these decompose rapidly even in the solid state, with fluorination of the ligands. The [VOF3(Ph3AsO)2] also decomposes in solutionto a mixture of products including Ph3AsF2 and [V6O12F4(Ph3AsO)2(Ph2AsO2)2] identified crystallographically. Comparisons with complexes of VOCl3 are also described.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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[VO2F(L-L)] (L-L = 2,2'-bipyridyl, 1,10-phenanthroline, Me2N(CH2)2NMe2) and [VO2F(py)2] (py = pyridine) have been prepared from the corresponding [VOF3(L-L)] or [VOF3(py)2] and O(SiMe3)2 in MeCN solution. VO2F (itself made from VOF3 and O(SiMe3)2 in MeCN) forms [Me4N][VO2F2] with [Me4N]F, but does not react with neutral N- or O-donor ligands. VO2Cl, prepared from VOCl3 and ozone, reacts with 2,2'-bipyridyl or 1,10-phenanthroline to form [VO2Cl(L-L)], with pyridine or pyridine-N-oxide (L) to produce [VO2Cl(L)2], and with OPPh3 or OAsPh3 (L') gives [VO2Cl(L')]. A second product from the OPPh3 system is the ionic [VO2(OPPh3)3][VO2Cl2] containing a trigonal bipyramidal cation. Neither VO2F nor VO2Cl form isolable complexes with MeCN, thf or MeO(CH2)2OMe, and both are reduced by P-, As-, S- or Se-donor ligands. [Ph4As][VO2X2] (X = F or Cl) react with 2,2'-bipyridyl to form [VO2X(2,2'-bipyridyl)], but similar reactions with weaker O-donor ligands fail. The complexes have been characterised by IR, multinuclear NMR (1H, 19F, 51V or 31P) and UV-visible spectroscopy. X-ray crystal structures are reported for [VO2F(py)2], [VO2Cl(L)2] (L = py or pyNO) and [VO2(OPPh3)3][VO2Cl2].