Inhaltszusammenfassung

Protolysis reactions of [VMeS3(THF)] with orthosubstituted phenols (2-iso-propyl-(H-IPP), 2-tert-butyl(H-TBP), 2,4,6-trimethylphenol (HOMes) and 2,2'biphenol (H-2-Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)(2)(THF)(2)] (OAr = IPP (1), TBP (2)), [VMeS2(OMes)(THF)] (4), [V(OAr)(3)(THF)(2)] (OAr = TBP (3), OMes (5)), and [V-2(Biphen)(3)(THF)(4)] (6). Treatment of 6 with Li(2)Biphen(Et2O)(4) results in formation of [(Li(OEt2)](3)V(Biphen)(3)] (7) and with MesL...Protolysis reactions of [VMeS3(THF)] with orthosubstituted phenols (2-iso-propyl-(H-IPP), 2-tert-butyl(H-TBP), 2,4,6-trimethylphenol (HOMes) and 2,2'biphenol (H-2-Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)(2)(THF)(2)] (OAr = IPP (1), TBP (2)), [VMeS2(OMes)(THF)] (4), [V(OAr)(3)(THF)(2)] (OAr = TBP (3), OMes (5)), and [V-2(Biphen)(3)(THF)(4)] (6). Treatment of 6 with Li(2)Biphen(Et2O)(4) results in formation of [(Li(OEt2)](3)V(Biphen)(3)] (7) and with MesLi complexes [(Li(THF)(2))(2)VMes(Biphen)(2)] . THF (8) and [(Li(DME)]- VMeS2(Biphen)] (9) are formed. Reacting [VCl3(THF)(3)] with LiOMes in 1:1 to 1:4 ratios yields the componds [VCl3-n(OMes)(n)(THF)(2)] (n = 1 (5b), 2 (5a), 3 (5)) and [(Li(DME)(2)]V(OMes)(4)] (5c), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [[Li(DME)n)(VMeS2(OAr)211 (OAr =: IPP (10), TBP (11), OMes (12) (n = 2 or 3) and [(Li(DME)(2)]-[VMes(OMeS)(3))] (15) are obtained by reaction of 1, 2, 5 a and 5 with MesLi. With [(Li(DME)(2)(THF)](VMeS3(IPP))] (13) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMeS3(THF)l forming [Li(THF)41[VMeS3(OMes)] (14) completes the series of [Li(solv.)(x)][VMes(4-n)-(OMes)(n)] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes(4-n)(OMes)(n)] derivatives 16, to 19 by reaction with p-chloranile. They were investigated by epr spectroscopy. The molecular structures of 1, 3, 5, 5 a, 5a-Br 7, 10 and 13 have been determined by X-ray analysis. In I (monoclinic, C2/c, a = 29.566(3) Angstrom, b 14.562(2) Angstrom, c = 15.313(1) Angstrom, beta = 100.21(1)degrees, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Angstrom, b = 14.549(3) Angstrom, c = 17.784(4) Angstrom, beta = 90.00degrees, Z = 8), (5) (triclinic, P(1) over bar, a = 8.868(1) Angstrom, b = 14.520(3) Angstrom, c = 14.664(3) Angstrom, alpha = 111.44(1)degrees, beta = 96.33(1)degrees, gamma = 102.86(1)degrees, Z = 2), 5a (monoclinic, P2(1)/c, a = 20.451(2) Angstrom, b = 8.198(1) Angstrom, c = 15.790(2) Angstrom, beta = 103.38(1)degrees, Z = 4) and 5a-Br (monoclinic, P2(1)/c, a = 21.264(3) Angstrom, b = 8.242(4) Angstrom, c = 15.950(2) Angstrom, beta = 109.14(1)degrees, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P(3) over bar c1, a = 20.500(3) Angstrom, b = 20.500(3) Angstrom, c = 18.658(4) Angstrom, Z = 6) has an octahedral environment. The three Li(OEt2)(+) fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2(1)/c, a = 16.894(3) Angstrom, b = 12.181(2) Angstrom, c = 25.180(3) Angstrom, beta = 91.52(1)degrees, Z = 4) and 13 (orthorhombic, Pna2(1), a 16.152(4) Angstrom, b = 17.293(6) Angstrom, c = 16.530(7) Angstrom, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively. » weiterlesen» einklappen

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