Journal article
Synthesis, Redox Chemistry, and Electronic Structures of Bis-di(silylamido)silane f-Element Complexes
Inorganic chemistry, Vol.64(43), pp.21465-21478
11/03/2025
DOI: 10.1021/acs.inorgchem.5c03345
PMID: 41114669
Abstract
We report the synthesis and characterization of pseudo-tetrahedral f-element complexes bearing the sterically demanding bidentate di(silylamido)silane ligand, {Me2Si(NSiiPr3)2}2- (Me2SiN†N†). Two equivalents of the dipotassium salt, [Me2SiN†N†K2] (1), react with either MIIII3(THF)n (M = Ce, Pr, n = 4; M = Tb, n = 3.5) or [UIV(BH4)4]n affording trivalent [MIII(Me2SiN†N†)2{K(toluene)2}]n (2M; M = Ce, Pr, Tb) and tetravalent [UIV(Me2SiN†N†)2] (3U), respectively. Complex 2Ce was oxidized to tetravalent [CeIV(Me2SiN†N†)2] (3Ce) with AgII, but 2Pr and 2Tb were unreactive under these conditions. The electrochemical accessibility of M(IV/III) couples in 2M (M = Ce, Pr, Tb) and 3M (M = Ce, U) was examined by cyclic voltammetry. For 2Ce and 3Ce, a quasi-reversible Ce(IV/III) couple was observed (Epc = -1.19 V vs [Fc]+/0), but complexes 2Pr and 2Tb showed anodic waves attributed to ligand oxidation only, which is supported by computational analyses. For complex 3U, U(IV/III), U(V/IV), and U(VI/V) redox couples with E1/2 values of -2.38, -0.89, and -0.11 V vs [Fc]+/0, respectively, were found. All complexes have been characterized variously by single-crystal X-ray diffraction, multinuclear NMR, UV-vis-NIR, and IR spectroscopies, SQUID magnetometry, and elemental analyses as appropriate. Electronic structure calculations were employed to rationalize electrochemical results for 2Pr, 2Tb, and 3Ce.We report the synthesis and characterization of pseudo-tetrahedral f-element complexes bearing the sterically demanding bidentate di(silylamido)silane ligand, {Me2Si(NSiiPr3)2}2- (Me2SiN†N†). Two equivalents of the dipotassium salt, [Me2SiN†N†K2] (1), react with either MIIII3(THF)n (M = Ce, Pr, n = 4; M = Tb, n = 3.5) or [UIV(BH4)4]n affording trivalent [MIII(Me2SiN†N†)2{K(toluene)2}]n (2M; M = Ce, Pr, Tb) and tetravalent [UIV(Me2SiN†N†)2] (3U), respectively. Complex 2Ce was oxidized to tetravalent [CeIV(Me2SiN†N†)2] (3Ce) with AgII, but 2Pr and 2Tb were unreactive under these conditions. The electrochemical accessibility of M(IV/III) couples in 2M (M = Ce, Pr, Tb) and 3M (M = Ce, U) was examined by cyclic voltammetry. For 2Ce and 3Ce, a quasi-reversible Ce(IV/III) couple was observed (Epc = -1.19 V vs [Fc]+/0), but complexes 2Pr and 2Tb showed anodic waves attributed to ligand oxidation only, which is supported by computational analyses. For complex 3U, U(IV/III), U(V/IV), and U(VI/V) redox couples with E1/2 values of -2.38, -0.89, and -0.11 V vs [Fc]+/0, respectively, were found. All complexes have been characterized variously by single-crystal X-ray diffraction, multinuclear NMR, UV-vis-NIR, and IR spectroscopies, SQUID magnetometry, and elemental analyses as appropriate. Electronic structure calculations were employed to rationalize electrochemical results for 2Pr, 2Tb, and 3Ce.
Details
- Title: Subtitle
- Synthesis, Redox Chemistry, and Electronic Structures of Bis-di(silylamido)silane f-Element Complexes
- Creators
- Benjamin L L Réant - University of ManchesterS Genevieve Duggan - University of IowaJohn A Seed - University of ManchesterPere Miró - University of IowaConrad A P Goodwin - University of Manchester
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.64(43), pp.21465-21478
- DOI
- 10.1021/acs.inorgchem.5c03345
- PMID
- 41114669
- NLM abbreviation
- Inorg Chem
- ISSN
- 1520-510X
- eISSN
- 1520-510X
- Publisher
- AMER CHEMICAL SOC
- Grant note
- Basic Energy SciencesRoyal Society: URF\211271 University Research Fellowship: EP/K039547/1, EP/V007580/1, EP/P001386/1, EP/W014521/1, EP/V035231/1, EPS033181/1 EPSRC: DE-SC0023477 US Department of Energy
We thank the Royal Society for funding Postdoctoral funding (B. L. L. R.) and a University Research Fellowship (URF\211271 to C.A.P.G.). We acknowledge funding from the EPSRC (EP/K039547/1, EP/V007580/1, and EP/P001386/1 for NMR spectroscopy and X-ray diffraction). We also thank the EPSRC UK EPR National Research Facility for access and use of the SQUID magnetometer (EP/W014521/1, EP/V035231/1, EPS033181/1). This work was supported by the US Department of Energy under Award DE-SC0023477. We thank Prof. Stephen Liddle for support (J.A.S.). We also thank Carlo Bawn for help with VT NMR data collection. Elemental analyses were performed at the UoM by Martin Jennings and Anne Davies. Bespoke glassware was produced by David Marshall and Steven Green at the University of Manchester.
- Language
- English
- Electronic publication date
- 10/20/2025
- Date published
- 11/03/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9985016012802771
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