BTBPs versus BTPhens: Some Reasons for Their Differences in Properties Concerning the Partitioning of Minor Actinides and the Advantages of BTPhens

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• 作者：Frank W. Lewis ; Laurence M. Harwood ; Michael J. Hudson ; Michael G. B. Drew ; V茅ronique Hubscher-Bruder ; Vladimira Videva ; Fran莽oise Arnaud-Neu ; Karel Stamberg ; Shyam Vyas
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 6, 2013
• 年：2013
• 卷：52
• 期：9
• 页码：4993-5005
• 全文大小：544K
• 年卷期：v.52,no.9(May 6, 2013)
• ISSN：1520-510X

文摘

Two members of the tetradentate N-donor ligand families 6,6鈥?bis(1,2,4-triazin-3-yl)-2,2鈥?bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe₄-BTPhen 2 has faster complexation kinetics than CyMe₄-BTBP 1. The values for the HOMO鈥揕UMO gap of 2 are comparable with those of CyMe₄-BTBP 1 for which the HOMO鈥揕UMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex 鈮?heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol^鈥?) energy barrier to rotation about the central biaryl C鈥揅 axis in order to achieve the cis鈥?i>cis conformation that is required to form a complex, whereas the cis鈥?i>cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe₄-BTPhen 2 with Y(NO₃)₃ is also reported. The metal ion is 10-coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)掳, 6.4(2)掳, 9.7(2)掳, respectively.