Synthesis, solid-state structure and multinuclear NMR studies of the new polyhydrido iridium carbonyl cluster Ir4H4(μ-H)4(CO)4(PPh3)4

被引:0
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作者
Garlaschelli, L
Greco, F
Peli, G
Manassero, M
Sansoni, M
Gobetto, R
Salassa, L
Della Pergola, R
机构
[1] Univ Milan, Dipartimento Chim Inorgan Metallorgan & Anali, I-20133 Milan, Italy
[2] Univ Milan, Dipartimento Chim Strutturale & Stereochim Inorga, I-20133 Milan, Italy
[3] Univ Turin, Dipartimento Chim Inorgan Chim Fis & Chim Mat, I-10125 Turin, Italy
[4] Univ Milan, Dipartimento Sci Ambiente & Terr, I-20126 Milan, Italy
关键词
cluster compounds; iridium; hydride ligands; NMR spectroscopy; P ligands;
D O I
暂无
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The carbonyl hydride cluster Ir4H8(CO)(4)(PPh3)(4) (1) has been formed in hig(31)P NMR spectra, two isomeric forms (1A and 1B) of the cluster are present in CD2Cl2 solution at room temperature, and they do not interconvert in the explored temperature range. However, if a solid sample of the cluster is dissolved at 188 K, only 1A is detected by NMR spectroscopy. The structure of 1B could be proposed on the basis of the T-1 relaxation times of the various hydrides: it results by localised exchange of H and CO around two vertices of the tetrahedral frame.h yield and purity by heating a mixture of Ir-4(CO)(12) and PPh3 in toluene at 90 degreesC under hydrogen at atmospheric pressure. The product has been characterised by microanalysis, spectroscopy (IR, H-1 and P-31 NMR) and X-ray diffraction. In the solid state one hydrogen, one CO and one triphenylphosphane ligand are terminally bonded to each iridium atom, whereas four hydride ligands are bridging. All the hydrogen atoms were directly located by X-ray analysis at an average H-Ir distance of 1.55 Angstrom. (for the terminal H) and 1.75 Angstrom (for the p-H). As shown by H-1 and P-31 NMR spectra, two isomeric forms (1A and 1B) of the cluster are present in CD2Cl2 solution at room temperature, and they do not interconvert in the explored temperature range. However, if a solid sample of the cluster is dissolved at 188 K, only 1A is detected by NMR spectroscopy. The structure of 1B could be proposed on the basis of the T-1 relaxation times of the various hydrides: it results by localised exchange of H and CO around two vertices of the tetrahedral frame. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
引用
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页码:2108 / 2112
页数:5
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