| Автор | Leung, Wa-Hung |
| Автор | Danopoulos, Andreas A. |
| Автор | Wilkinson, Geoffrey |
| Автор | Hussain-Bates, Bilquis |
| Автор | Hursthouse, Michael B. |
| Дата выпуска | 1991 |
| dc.description | The compound Cr(NBu<sup>t</sup>)Cl3, isolated as its adducts with tetrahydrofuran (thf) and 1,2-dimethoxyethane (dme), has been prepared by chlorination of Cr(NBu<sup>t</sup>)2Cl2. These materials have been used as sources of other chromium compounds such as the neutral adducts Cr(NBu<sup>t</sup>)Cl3(PR3)2(R3= Me3, Et3, Me2Ph or EtPh2) or Cr(NBu<sup>t</sup>)Cl2(NC7H13)(NC7H13= quinuclidine) or anionic complexes such as [PPh4][Cr(NBu<sup>t</sup>)Cl4]. The tertiary phosphine complexes in the presence of excess of phosphine are photochemically or thermally reduced to CrCl3(PR3)3 and the tertiary phosphinimine. Halide-substitution reactions on Cr(NBu<sup>t</sup>)Cl3(dme) or [Cr(NBu<sup>t</sup>)Cl4]<sup>â </sup> with O,N, (O,N) and S ligands give rise to compounds such as cis-Cr(NBu<sup>t</sup>)Cl(OC9H6N)2(OC9H6N = quinolin-8-olate), [Cr(NBu<sup>t</sup>)(mnt)2]<sup>â </sup>(mnt = maleonitriledithiolate) and Cr(NBu<sup>t</sup>)Cl(S2CNEt2)2; cyclic voltammetry of the last two complexes is reported. Evidence for the disproportionation 2Cr<sup> V </sup>â Cr<sup> VI </sup>+ Cr<sup> IV </sup> in reactions of alkoxides is given. Reduction of Cr(NBu<sup>t</sup>)Cl3(dme) in the presence of 1,2-bis(dimethylphosphino)ethane (dmpe) gives the chromium(IV) species [Cr(NBu<sup>t</sup>)(dmpe)2Cl]Cl. The EPR (X-band) spectra of chromium(V) species at room temperature show hyperfine splitting for <sup>53</sup>Cr, <sup>14</sup>N and <sup>31</sup>P in appropriate compounds with g iso values at 77 K of ca. 2.00. The compounds [V(NBu<sup>t</sup>)(NHBu<sup>t</sup>)(µ-NBu<sup>t</sup>)]2 and [V(µ-NBu<sup>t</sup>)(OSiMe3)2]2 are also described. The X-ray structures of five compounds have been determined: Cr(NBu<sup>t</sup>)Cl3(dme) is octahedral with a mer arrangement of the three chlorines; Cr[C6H4(NH)2-o]Cl2(PMe2Ph)2 is also octahedral, having C 2 symmetry with trans phosphines and cis chlorines; Cr(NBu<sup>t</sup>)2(OSiPh3)2 is distorted tetrahedral; Cr(NBu<sup>t</sup>)Cl(OC9H6N)2 is octahedral with the chelating quinolin-8-olato groups arranged to give trans O,O and cis N,N geometry; and [Cr(NBu<sup>t</sup>)(mnt)2]<sup>â </sup> has a square-pyramidal structure with an axial imido group. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | tert-Butylimido complexes of chromium and vanadium. X-Ray crystal structures of Cr(NBut)Cl3(MeOCH2CH2OMe), Cr[C6H4(NH)2-o]Cl2(PMe2Ph)2, Cr(NBut)2(OSiPh3)2, Cr(NBut)-Cl(OC9H6N)2 and [(PPh3)2][Cr(NBut){S2C2(CN)2}2] |
| Тип | research-article |
| DOI | 10.1039/DT9910002051 |
| Electronic ISSN | 1364-5447 |
| Print ISSN | 1472-7773 |
| Журнал | Journal of the Chemical Society, Dalton Transactions |
| Первая страница | 2051 |
| Последняя страница | 2061 |
| Выпуск | 8 |
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