X-ray and NOE Studies on Trinuclear Iridium Hydride Phosphino Oxazoline (PHOX) Complexes
X-ray and NOE Studies on Trinuclear Iridium Hydride Phosphino Oxazoline (PHOX) Complexes
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DOI：
10.1021/om020805a
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发表时间：
2003-02
期刊：
影响因子：
2.8
通讯作者：
S. P. Smidt;A. Pfaltz;Eloísa Martínez-Viviente;P. Pregosin;A. Albinati
中科院分区：
文献类型：
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作者：
S. P. Smidt;A. Pfaltz;Eloísa Martínez-Viviente;P. Pregosin;A. Albinati
两个[Ir_3（μ ~ 3-H）（H）_6（PHOX）_3] X_1X_2型三核铱氢化物簇合物（X1 = PF6，X2 = OTf; X1 = X2 = PF6; X1 = X2 = OTf; PHOX =（S）-4-叔丁基-2-[2-（2-甲基-IH-吡唑-4-基）-IH-吡唑-4-基]-IH-吡唑（S）-2-[2-（三氟甲基）苯基]-4，5-二氢恶唑[（二苯基膦基）苯基]-4-异丙基-4，5-二氢恶唑），并通过X射线衍射和多维核磁共振进行了表征。它们含有一个单一的桥接氢化物在伪反式位置的P-供体。络合的PHOX配体揭示了一个手性口袋，涉及一个pseudoequatorial P-芳基取代基和一个pseudoaxial（接近恶唑啉取代基）P-芳基。这些三核配合物被证明是无活性的氢化催化剂。
Two trinuclear iridium hydride clusters of the type [Ir3(μ3-H)(H)6(PHOX)3]X1X2 (X1 = PF6, X2 = OTf; X1 = X2 = PF6; X1 = X2 = OTf; PHOX = (S)-4-tert-butyl-2-[2-(di-o-tolylphosphinyl)phenyl]-4,5-dihydrooxazole, (S)-2-[2-(diphenylphosphinyl)phenyl]-4-isopropyl-4,5-dihydrooxazole) have been prepared and characterized by X-ray diffraction and multidimensional NMR. They contain a single bridging hydride in pseudo-trans position to the P-donors. The complexed PHOX ligands reveal a chiral pocket involving one pseudoequatorial P-aryl substituent and one pseudoaxial (proximate to the oxazoline substituent) P-aryl group. These trinuclear complexes are shown to be inactive as hydrogenation catalysts.