Reactions of Os(5-C5H5)Cl(PiPr3)2 with NH=CPh2 and

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• 作者：Miguel A. Esteruelas ; Enrique Guti&eacute ; rrez-Puebla ; Ana M. Ló ; pez ; Enrique Oñ ; ate ; and Jos&eacute ; I. Tolosa
• 刊名：Organometallics
• 出版年：2000
• 出版时间：February 7, 2000
• 年：2000
• 卷：19
• 期：3
• 页码：275 - 284
• 全文大小：221K
• 年卷期：v.19,no.3(February 7, 2000)
• ISSN：1520-6041

文摘

The cyclopentadienyl complex Os(⁵-C₅H₅)Cl(PⁱPr₃)₂ (1) reacts with benzophenone imineto give the cationic orthometalated derivative [OsH(⁵-C₅H₅){NH=C(Ph)C₆H₄}(PⁱPr₃)]Cl (2a),containing the hydride ligand and the metalated phenyl group mutually cisoid disposed.Treatment of 2a with NaOCH₃ affords the neutral species Os(⁵-C₅H₅){NH=C(Ph)C₆H₄}(PⁱPr₃) (3), which by protonation with HBF₄·OEt₂ gives [OsH(⁵-C₅H₅){NH=C(Ph)C₆H₄}(PⁱPr₃)]BF₄ (4). The structure of 4 was determined by an X-ray investigation. The geometryaround the osmium center can be described as a four-legged piano-stool geometry, with thehydride ligand transoid disposed to the metalated phenyl group and cisoid to the NH of theimine. The separation between the hydride and the NH hydrogen atom is about 2.5 Å.Complex 1 also reacts with triphenylphosphine. In this case the reaction product is the mixed-ligand compound Os(⁵-C₅H₅)Cl(PPh₃)(PⁱPr₃) (5). Treatment of 5 with TlPF₆ affords theorthometalated triphenylphosphine derivative [OsH(⁵-C₅H₅)(PPh₂C₆H₄}(PⁱPr₃)]PF₆ (6). Thestructure of 6 was also determined by an X-ray investigation. As for 4, the geometry aroundthe osmium center can be described as a four-legged piano-stool geometry with the hydrideligand and the metalated phenyl group in transoid positions. Treatment of 6 with NaOCH₃produces the extraction of the hydride ligand and the formation of the neutral species Os(⁵-C₅H₅)(PPh₂C₆H₄)(PⁱPr₃) (7), which in methanol under reflux gives OsH(⁵-C₅H₅)(PPh₃)(PⁱPr₃) (8). Protonation of 8 with HBF₄·OEt₂ affords the cationic dihydride [OsH₂(⁵-C₅H₅)(PPh₃)(PⁱPr₃)]BF₄ (9).