Preparation, Spectroscopic Characterization, X-ray Structure, and Theoretical Investigation of Hydride-, Dihydrogen-, and Acetone-OsTp Complexes: A Hydridotris(pyrazolyl)borate-Cyclopentadienyl Compar
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- 作者：Ruth Castro-Rodrigo ; Miguel A. Esteruelas ; Ana M. Ló ; pez ; Montserrat Olivá ; n ; Enrique Oñ ; ate
- 刊名：Organometallics
- 出版年：2007
- 出版时间：August 27, 2007
- 年：2007
- 卷：26
- 期：18
- 页码：4498 - 4509
- 全文大小：452K
- 年卷期：v.26,no.18(August 27, 2007)
- ISSN：1520-6041
文摘
Complex OsH3Cl(PiPr3)2 (1) reacts with KTp (Tp = hydridotris(pyrazolyl)borate) in tetrahydrofuranat room temperature to give OsH3(
2-Tp)(PiPr3)2 (2). In toluene at 80 
C, the 2-Tp complex 2 istransformed to the 3-Tp derivative OsH3Tp(PiPr3) (3) in quantitative yield after 7 h. Protonation of 3with HBF4 affords the bis(dihydrogen) compound [OsTp(
2-H2)2(PiPr3)]BF4 (4). In acetone complex 4releases the coordinated hydrogen molecules in a sequential manner. At room temperature, the dihydrogen-solvate complex [OsTp(2-H2)(1-OCMe2)(PiPr3)]BF4 (5) is formed, while at 56 C the loss of bothhydrogen molecules gives rise to the bis-solvento derivative [OsTp(1-OCMe2)2(PiPr3)]BF4 (6). Complexes2-6 have been characterized by X-ray diffraction analysis, and DFT calculations support their formulation.The structures of 3-5 have been compared with those of their Cp counterparts OsH3Cp(PiPr3), [OsH2Cp(2-H2)(PiPr3)]BF4, and [OsH2Cp(1-OCMe2)(PiPr3)]BF4. The results show that the Tp ligand avoidspiano stool geometries, while it enforces dispositions allowing N-Os-N angles close to 90 such asoctahedron and pentagonal bipyramid.
2-Tp)(PiPr3)2 (2). In toluene at 80 C, the 2-Tp complex 2 istransformed to the 3-Tp derivative OsH3Tp(PiPr3) (3) in quantitative yield after 7 h. Protonation of 3with HBF4 affords the bis(dihydrogen) compound [OsTp(2-H2)2(PiPr3)]BF4 (4). In acetone complex 4releases the coordinated hydrogen molecules in a sequential manner. At room temperature, the dihydrogen-solvate complex [OsTp(2-H2)(1-OCMe2)(PiPr3)]BF4 (5) is formed, while at 56 C the loss of bothhydrogen molecules gives rise to the bis-solvento derivative [OsTp(1-OCMe2)2(PiPr3)]BF4 (6). Complexes2-6 have been characterized by X-ray diffraction analysis, and DFT calculations support their formulation.The structures of 3-5 have been compared with those of their Cp counterparts OsH3Cp(PiPr3), [OsH2Cp(2-H2)(PiPr3)]BF4, and [OsH2Cp(1-OCMe2)(PiPr3)]BF4. The results show that the Tp ligand avoidspiano stool geometries, while it enforces dispositions allowing N-Os-N angles close to 90 such asoctahedron and pentagonal bipyramid.