Coordination Chemistry of 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane: Preparation and Characterization of Ru(II) Complexes
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- 作者：Evan E. Joslin ; Claire L. McMullin ; T. Brent Gunnoe ; Thomas R. Cundari ; Michal Sabat ; William H. Myers
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：April 16, 2012
- 年：2012
- 卷：51
- 期：8
- 页码：4791-4801
- 全文大小：480K
- 年卷期：v.51,no.8(April 16, 2012)
- ISSN：1520-510X
文摘
The complexes TpRu[P(OCH2)2(OCCH3](PPh3)Cl (2) [Tp = hydridotris(pyrazolyl)borate; P(OCH2)2(OCCH3) (1) = (4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane] and TpRu(L)(PPh3)Cl [L = P(OCH2)3CEt (3), PMe3 (4) or P(OMe)3 (5)], (畏6-C6H6)Ru(L)Cl2 [L = PPh3 (6), P(OMe)3 (7), PMe3 (8), P(OCH2)3CEt (9), CO (10) or P(OCH2)2(OCCH3) (11)] and (畏6-p-cymene)Ru(L)Cl2 [L = P(OCH2)3CEt (12), P(OCH2)2(OCCH3)P(OCH2)2(OCCH3) (13), P(OMe)3 (14) or PPh3 (15)] have been synthesized, isolated, and characterized by NMR spectroscopy, cyclic voltammetry, mass spectrometry, and, for some complexes, single crystal X-ray diffraction. Data from cyclic voltammetry and solid-state structures have been used to compare the properties of (1) with other phosphorus-based ligands as well as carbon monoxide. Data from the solid-state structures of Ru(II) complexes show that P(OCH2)2(OCCH3) has a cone angle of 104掳. Cyclic voltammetry data reveal that the Ru(II) complexes bearing P(OCH2)2(OCCH3) have more positive Ru(III/II) redox potentials than analogous complexes with the other phosphorus ligands; however, the Ru(III/II) potential for (畏6-C6H6)Ru[P(OCH2)2(OCCH3)]Cl2 is more negative compared to the Ru(III/II) potential for the CO complex (畏6-C6H6)Ru(CO)Cl2. For the Ru(II) complexes studied herein, these data are consistent with the overall donor ability of 1 being less than other common phosphines (e.g., PMe3 or PPh3) or phosphites [e.g., P(OCH2)3CEt or P(OMe)3] but greater than carbon monoxide.