TY - JOUR
T1 - Uranium(III) and Uranium(IV) meta-Terphenylthiolate Complexes
AU - Réant, Benjamin L.L.
AU - Seed, John A.
AU - Whitehead, George F.S.
AU - Goodwin, Conrad A.P.
N1 - Publisher Copyright:
© 2025 The Authors. Published by American Chemical Society.
PY - 2025/2/24
Y1 - 2025/2/24
N2 - We report the synthesis and characterization of crystalline m-terphenylthiolate uranium complexes supported by the bulky ligand system, SAriPr6 (SAriPr6 = {SC6H3-2,6-(Tripp)2}; Tripp = 2,4,6-iPr-C6H2). Treatment of UIVCl4 with 2 equiv of KSAriPr6 in Et2O afforded both [UIV(SAriPr6)2(Cl)2] (1) and the Et2O adduct, [UIV(SAriPr6)2(Cl)2(Et2O)2] (1·Et2O) in poor yield. The reaction between [UIV(BH4)4] and 1 equiv of KSAriPr6 in toluene gave several crystals of the double salt, [UIV(μ-SAriPr6)(BH4)2(μ-BH4)(μ3-BH4)K]2 (2), and exposing the crude reaction mixture to Et2O gave the disulfide dimer, (SAriPr6)2. The reaction between [UIV(BH4)4] and 1 equiv of HSAriPr6 in hot toluene gave [UIII(H3B·SAriPr6 κS,H,H)(BH4)2] (3) which proved resistant to further substitution using either HSAriPr6 or KSAriPr6. Two U(III) mono-terphenylthiolates, [UIII(SAriPr6)(BH4)2] (4a) and [{UIII(SAriPr6)(BH4)}2{μ-B2H6}] (4b), were isolated as a mixture from the reaction between [UIII(BH3)3(toluene)] and 1 equiv of KSAriPr6, while using 2 equiv of KSAriPr6 gave the bis-terphenylthiolate complex [UIII(SAriPr6)2(BH4)] (5). Complex 4b is a rare example of a nidometalloborane. Complexes 1−5 have been characterized variously by single-crystal and powder X-ray diffraction, multinuclear NMR spectroscopy, infrared spectroscopy, UV−Vis−NIR spectroscopy, SQUID magnetometry, and elemental analyses as appropriate. Quantum chemical calculations have been employed to interpret the nature of the U−S bonding interactions across these complexes.
AB - We report the synthesis and characterization of crystalline m-terphenylthiolate uranium complexes supported by the bulky ligand system, SAriPr6 (SAriPr6 = {SC6H3-2,6-(Tripp)2}; Tripp = 2,4,6-iPr-C6H2). Treatment of UIVCl4 with 2 equiv of KSAriPr6 in Et2O afforded both [UIV(SAriPr6)2(Cl)2] (1) and the Et2O adduct, [UIV(SAriPr6)2(Cl)2(Et2O)2] (1·Et2O) in poor yield. The reaction between [UIV(BH4)4] and 1 equiv of KSAriPr6 in toluene gave several crystals of the double salt, [UIV(μ-SAriPr6)(BH4)2(μ-BH4)(μ3-BH4)K]2 (2), and exposing the crude reaction mixture to Et2O gave the disulfide dimer, (SAriPr6)2. The reaction between [UIV(BH4)4] and 1 equiv of HSAriPr6 in hot toluene gave [UIII(H3B·SAriPr6 κS,H,H)(BH4)2] (3) which proved resistant to further substitution using either HSAriPr6 or KSAriPr6. Two U(III) mono-terphenylthiolates, [UIII(SAriPr6)(BH4)2] (4a) and [{UIII(SAriPr6)(BH4)}2{μ-B2H6}] (4b), were isolated as a mixture from the reaction between [UIII(BH3)3(toluene)] and 1 equiv of KSAriPr6, while using 2 equiv of KSAriPr6 gave the bis-terphenylthiolate complex [UIII(SAriPr6)2(BH4)] (5). Complex 4b is a rare example of a nidometalloborane. Complexes 1−5 have been characterized variously by single-crystal and powder X-ray diffraction, multinuclear NMR spectroscopy, infrared spectroscopy, UV−Vis−NIR spectroscopy, SQUID magnetometry, and elemental analyses as appropriate. Quantum chemical calculations have been employed to interpret the nature of the U−S bonding interactions across these complexes.
UR - https://www.scopus.com/pages/publications/85217213308
U2 - 10.1021/acs.inorgchem.4c03085
DO - 10.1021/acs.inorgchem.4c03085
M3 - Article
C2 - 39919254
AN - SCOPUS:85217213308
SN - 0020-1669
VL - 64
SP - 3161
EP - 3177
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 7
ER -