Specific sequestering agents for the actinides. 8. synthesis and structural chemistry of tetrakis(thiohydroxamato) hafnium(IV) in Hf(CH/sub 3/C/sub 6/H/sub 4/(S)N(O)C/sub 3/)/sub 4/. C/sub 2/H/sub 5/OH

Journal Article · Thu Apr 01 04:00:00 EST 1982 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00134a082· OSTI ID:5226007

Abu-Dari, K; Raymond, K

A continuing project in this laboratory has been the design and synthesis of specific sequestering agents for the actinide IV ions. The degree of success so far achieved in this goal has been reviewed recently. The approach used relies on the similar coordination chemistry of high-spin Fe/sup 3 +/ and Pu and the molecular architecture of the siderophores (ferric ion specific chelating agents of microbial origin). While hydroxamate and catecholate chealating groups are the primary functional groups in siderophores, the thiohydroxamate chelating unit also occurs in at least one compound of natural origin. The tetrakis(catecholato)metalate(IV) complexes of Th(IV), U(IV), and Hf(IV) have all been prepared and structurally characterized. They are isostructural, with the D/sub 2d/ coordination symmetry of the trigonal-faced dodecahedron. Both the hydroxamate complexes tetrakis(N-isoproply-3,3-dimethylbutanehydroxamato)hafnium(IV)/sup 2/ and tetrakis(N-phenylbenzohydroxamato)hafnium(IV)/sup 9/ have this same D/sub 2d/ geometry. In contrast, the more sterically hindered complex, tetrakis(N-isopropyl-2,3-dimethylpropanehydroxamato)thorium(IV), is distorted substantially toward a cubic coordination polyhedron. No tetrakis(thiohydroxamate) complexes have been structurally characterized to date. Determination of the coordination geometry of the unconstrained tetrakis(bidentate)metalate(IV) complexes are a fundamental component in the design of an octadentate chelating agent that incorporates four such functionalities to form an optimum metal coordination environment. While we have prepared thiohydroxamate complexes of Th(IV), no crystals suitable for structural analysis have been obtained. Instead, we report the synthesis and structural characterization of the hafnium complex, the title compound.

• Research Organization: Univ. of California, Berkeley
• OSTI ID: 5226007
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:4; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTINIDES
BOND ANGLE
BOND LENGTHS
CHELATING AGENTS
CHEMICAL ANALYSIS
CHEMICAL PREPARATION
COMPLEXES
CRYSTALS
DATA
DIMENSIONS
ELEMENTS
EXPERIMENTAL DATA
HAFNIUM COMPLEXES
INFORMATION
LENGTH
METALS
NUMERICAL DATA
PARAMETRIC ANALYSIS
QUALITATIVE CHEMICAL ANALYSIS
QUANTITATIVE CHEMICAL ANALYSIS
SEPARATION PROCESSES
STEREOCHEMISTRY
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES