- Novel triaikylstlbane iridium(I) and iridium(III) complexes including the X-ray crystal structure of five-coordinate [IrCl(C2H4)2(SbiPr3)2]
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The reaction of [IrCl(C8H14)2]2 (2) with SbiPr3 in the presence of H2 yields the dihydridoiridium(III) complex cis,mer[IrH2Cl(SbiPr3)3] (3) which on treatment with CO and with HC≡CR (R = Ph, CO2Me) affords the octahedral derivatives [IrH2Cl(CO)(SbiPr3)2] (4) and [IrHCl(C=CR)(SbiPr3)3] (5, 6), respectively. The stibane ligand trans to hydride in 5 and 6 is rather labile and, therefore, 5 and 6 react with pyridine to give [IrHCl(C=CR)(py)(SbiPr3))2] (7, 8). Five-coordinate bis-(stibane)iridium(I) complexes [IrCl(C2H4)2(SbR3)2] (10-12) were prepared from [IrCl(C2H4)2]2 (9) and four equiv. of SbR3 (R = iPr, Me, Ph). The X-ray crystal structural analysis of 10 reveals a distorted trigonal-bipyramidal geometry around the metal center with one stibane ligand and the two olefinic ligands in the equatorial plane. Compound 10 reacts with NaC5H5 to yield [C5H5Ir(C2H4)(SbiPr3)] (13) and with different alkynes by partial or complete displacement of the ethene ligands to give trans-[IrCl(PhC≡CPh)(SbiPr3)2] (14), [IrHCl(C≡CTol)(C2H4)(SbiPr3)2] (15), and trans-[IrCl-{ = C = C(SiMe3)R}(SbiPr3)2] (16, 17), respectively. VCH Verlagsgescllschaft mbH 1996.
- Werner, Helmut,Ortmann, Dagmara A.,Gevert, Olaf
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p. 411 - 417
(2007/10/03)
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- DARSTELLUNG UND SPECTROSKOPISCHE UNTERSUCHUNGEN VON METHYL- UND ISOPROPYLANTIMONHALOGENIDEN
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Halogenations of iPr3Sb yield the dihalides iPr3SbX2 X=Cl, Br, I.These compounds decompose thermally to iPrX and iPr2SbX.Halogenations of iPr2SbX produce unstable trihalides iPr2SbX3, which eliminate iPrX to give iPrSbX2.By this procedure only the bromides and iodides iPr2SbX and iPrSbX2 X=Br, I can be obtained in useful yields and purities.Pure iPrSbCl2 and iPr3Sb are products of exchange reaction of iPr2SbCl.The purity of the known methylcompounds Me2SbX X=Cl, Br, I obtained by decomposition of Me3SbX2 has been examined.MeSbI2 and Me3Sb are formed from Me2SbI.Previously unpublished ir-, 1H-nmr-, and ms-data of iPr3SbX2, R2SbX and RSbX2 R=Me, iPr, X=Cl, Br, I are discussed.
- Breunig, H. J.,Kanig, W.
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p. 149 - 160
(2007/10/02)
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