THESIS
2001
xxiii, 177 leaves : ill. ; 30 cm
Abstract
Reaction of [OsO
4] with C
7H
7MgBr (C
7H
7 = 2-methylphenyl) followed by column chromatography afforded the reported osmium tetraaryl [Os(C
7H
7)
4] along with the oxo-osmium(VI) [OsO(C
7H
7)
2] (1) and the dioxo-osmium(VI) [OsO
2(C
7H
7)
4] (2) complexes. Treatment of [OsO
4] with C
8H
9MgBr (C
8H
9 = 2,5-dimethylphenyl) gave a mixture of [Os(C
8H
9)
4] (3) and [OsO(C
8H
9)
4] (4) while that with C
8H
9OMgBr (C
8H
9O = 4-methoxy-2-methylphenyl) afforded [OsO(C
8H
9O)
4] (5). Oxidation of 3 with 3-chloroperoxybenzoic acid afforded 4 in good yield. The solid-state structures of 1 and 4 have been established by X-ray crystallography.
8 9 4 3 3 8 9 8 8 3 8 9 3 8 8...[
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Reaction of [OsO
4] with C
7H
7MgBr (C
7H
7 = 2-methylphenyl) followed by column chromatography afforded the reported osmium tetraaryl [Os(C
7H
7)
4] along with the oxo-osmium(VI) [OsO(C
7H
7)
2] (1) and the dioxo-osmium(VI) [OsO
2(C
7H
7)
4] (2) complexes. Treatment of [OsO
4] with C
8H
9MgBr (C
8H
9 = 2,5-dimethylphenyl) gave a mixture of [Os(C
8H
9)
4] (3) and [OsO(C
8H
9)
4] (4) while that with C
8H
9OMgBr (C
8H
9O = 4-methoxy-2-methylphenyl) afforded [OsO(C
8H
9O)
4] (5). Oxidation of 3 with 3-chloroperoxybenzoic acid afforded 4 in good yield. The solid-state structures of 1 and 4 have been established by X-ray crystallography.
Direct functionalization of osmium(IV) tetraaryl complex [Os(C
8H
9)
4] was studied. Reaction of 3 with CH
3COCl and AlCl
3 yielded [Os(C
8H
9)(C
8H
8-COMe-p)
3] 10 and [Os(C
8H
9)
3C
8H
8-COMe-p)] 11. Formylation of 3 with [TiCl
4] and dichloromethyl methyl ether yielded [Os(C
8H
9)
3(C
8H
8-CHO-p)] 12 and [Os(C
8H
9)
2(C
8H
8-CHO-p)
2] 13. Bromination of 3 with pyridinium tribromide in the presence of Fe powder to give [Os(C
8H
8-Br-p)
4] 15, which undergoes Suzuki coupling with arylboronic acids to afford a series of homoleptic functionalised aryls of osmium(IV).
Ir(III) orthometallated complexes [Ir
2Cl
2L
4], (L = 4'-substituted 2-phenylpyridine Rppy), reacted with S-donor ligands to form monomeric [Ir(t-Buppy)(S^S)] (S^S = Et
2NCS
2- and (MeO)
2PS
2-).
Treatment of lithium (4-oxazolinyl)phenyl prepared in situ from bromo(4-oxazolinyl)benzene and nBuLi with [Au(PPh
3)Cl] and [Pt(COD)Cl
2] (COD = 1,5 -cyclooctadiene) gave oxazolinylphenyl gold(I) and oxazolinylphenyl platinum(II) complexes respectively. These (oxazolinyl)phenyl complexes are capable for binding metal ions such as Pd(II), Zn(II) to give dinuclear and trinuclear complexes.
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