Synthesis, Properties, and Reactions of Monosulfonated Triphenylphosphine (PPh2(m-C6H4SO3K) = TPPMS) Complexes of Iridium(I). Crystal and Molecular S
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- 作者：Paul J. Roman ; Jr. ; David P. Paterniti ; Ronald F. See ; Melvyn Rowen Churchill ; and Jim D. Atwood
- 刊名：Organometallics
- 出版年：1997
- 出版时间：April 1, 1997
- 年：1997
- 卷：16
- 期：7
- 页码：1484 - 1490
- 全文大小：159K
- 年卷期：v.16,no.7(April 1, 1997)
- ISSN：1520-6041
文摘
Iridium complexes containing the TPPMS ligand (TPPMS =PPh2(m-C6H4SO3K))havebeen prepared and studied in DMSO and H2O as a comparisonto the PPh3 analogues intoluene. Measurements of the pH of the complexes show that mostare almost neutral, butIr(CO)(H)(TPPMS)3 is basic (pH = 10.7).The basicity of Ir(CO)(H)(TPPMS)3 isconfirmedby its reaction with H2O to giveIr(CO)(H)2(TPPMS)3+.In aqueous solution, reaction of trans-Ir(CO)(OH)(TPPMS)2 with H2 producesonlyfac-Ir(CO)(H)3(TPPMS)2not the usual mixtureof facial and meridional isomers. This is attributed to ahydrogen-bonding interactionbetween the two cis-TPPMS ligands in H2O.Reaction oftrans-Ir(CO)(Cl)(TPPMS)2withCO in water produces[Ir(CO)2(TPPMS)2+]Cl-and[Ir(CO)3(TPPMS)2+]Clsequentially in areaction that is pH dependent. Reaction oftrans-Ir(CO)(OH)(TPPMS)2 with COresults inproducts based on the water gas shift-reaction. These complexes ofTPPMS are spectroscopically very similar to the PPh3 analogues, but displaysignificantly different reactions in H2O.