高等学校化学学报

高等学校化学学报 ›› 1999, Vol. 20 ›› Issue (10): 1589.

• 论文 • 上一篇    下一篇

酸碱存在下水溶性铑膦配合物的NMR表征及氢甲酰化性能研究

张宇, 袁友珠, 廖新丽, 叶剑良, 姚春香, 蔡启瑞   

  1. 厦门大学化学系, 厦门 361005
  • 收稿日期:1998-09-01 出版日期:1999-10-24 发布日期:1999-10-24
  • 通讯作者: 袁友珠
  • 作者简介:张宇,男,27岁,博士.
  • 基金资助:

    国家自然科学基金(批准号:29873037);中国石油化学总公司联合资助“九五”重大项目(批准号:29792075).

NMR Characterization and Catalytic Hydroform ylation of Water-Soluble Rhodium-Phosphine Com plex in the Presence of Acid and Base

ZHANG Yu, YUAN You-Zhu, LIAO Xin-Li, YE Jian-Liang, YAO Chun-Xiang, TSAI Khirui   

  1. Department of Chemistry, Institute of Physical Chemistry, State Key Laboratory of Physical Chemistry for the Solid Surface, Xiamen University, Xiamen 361005, China
  • Received:1998-09-01 Online:1999-10-24 Published:1999-10-24

PDF (PC)

被引次数

9

摘要： 31P(1H)NMR和1HNMR研究表明,当NaOH加入到水溶性铑膦配合物HRh(CO)·(TPPTS)3[TPPTS:P(m-C6H4SO3Na)3]后,可观察到有少量的OTPPTS[OTPPTS:O=P(m-C6H4SO3Na)3]出现,但配合物的特征谱峰即使在高浓度的NaOH存在下也基本保持不变,表明NaOH对配合物分子结构的影响较小;当吡啶加入到HRh(CO)(TPPTS)3中,31P(1H)NMR谱图中出现游离配体TPPTS的31P谱峰及若干结构未知的新水溶性配合物的31P谱峰,表明吡啶分子将与配合物分子中的配体TPPTS发生配体交换反应.在HRh(CO)(TPPTS)3中分别加入一定量的HCl,HNO3,H2SO4和H3PO4等无机酸时,随着酸量的增加,配合物的31P物种含量逐渐下降,而OTPPTS量明显上升,直至配合物31P物种完全消失;高浓度乙酸对配合物结构的影响与上述无机酸类似.HRh(CO)(TPPTS)3的1-己烯氢甲酰化催化反应结果表明,碱存在下可获得较高的正异构醛比值,但催化活性降低;酸存在下所得产物正异构醛比值相对较低且呈淡黄色.

关键词: 31P(1H)NMR, 1HNMR, HRh(CO)(TPPTS)3, 酸碱性, 氢甲酰化

Abstract: When NaOH was added into D2O-solution of HRh(CO)(TPPTS)3[TPPTS: P(m-C6H4SO3Na)3, trisodium salt of tri-(m-sulfophenyl)-phosphine], there were no changes in the characteristic peaks for the w ater-soluble com plex although a sm allpeak at δ35.1 for OTPPTS[OTPPTS: O=P(m-C6H4SO3Na)3, trisodium salt of tri-(m-sulfophenyl)-phos-phine oxide] was formed undera high concentration of NaOH, as evidenced by the spectra of 31P(1H)NMR and 1HNMR, indicating thatthe influence on the m olecular structure ofthe com plex by NaOH may be limited. Severalnew signals at δ29_ 34 accom panied by the ap-pearance of free ligand TPPTSat δ-5.0_-5.3 appeared in the 31P(1H)NMR spectra w hen pyridine w as introduced into HRh(CO)(TPPTS)3, probably due to the reaction of lig-and exchange am ong the coordinated ligands(such as TPPTS, hydrogen, and CO) in the com plex HRh (CO)(TPPTS)3and pyridine m olecule. The w ater-soluble com plex can be readily decom posed, how ever, w hen inorganic acids such as HCl, H2SO4, HNO3and H3PO4w ere introduced into the D2O-solution of HRh(CO)(TPPTS)3, as show n in 31P(1H)NMR spectroscopic data. The decom position of the com plex was com pleted by the form ation of OTPPTS atδ35.1 and som e new phosphate species atδ27_ 29 in the 31P(1H)NMR spectra in the presence ofabove inorganic acids. Analogous results to those by addition ofinorganic acid w ere obtained w hen acetate acid w as exceeded in m ole ratio to HRh(CO)(TPPTS)3An increm entin n/iratio ofheptylaldehydes and a depression in TOF were obtained in case of the addition ofbase, in contrary, a low er n/iratio ofaldehydesin yellow ish productw as ob-tained in case of the addition of acid in 1-hexene hydroform ylation catalyzed by HRh(CO)(TPPTS)3.The results obtained show ed thatthe m olecularstructure and catalytic perform ance of HRh·(CO)(TPPTS)3may be affected by acid more disserviceably than by base.

Key words: 31P(1H)NMR, 1HNMR, HRh(CO)(TPPTS)3, Acidity and basicity, Hydro-form ylation

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