Sterically encumbered mixed sandwich compounds of uranium(III): synthesis and reactivity with small molecules
Rachel J. Kahan,Joy H. Farnaby,Joy H. Farnaby,Nikolaos Tsoureas,F. Geoffrey N. Cloke,Peter B. Hitchcock,Martyn P. Coles,S. Mark Roe,Claire Wilson +8 more
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TL;DR: A series of uranium(III) mixed sandwich complexes with sterically demanding CpR ligands, of the type [U(COTTIPS2)(CpR)] were synthesized and their X-ray crystal structures determined as discussed by the authors.
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About: This article is published in Journal of Organometallic Chemistry. The article was published on 15 Feb 2018. and is currently open access. The article focuses on the topics: Reactivity (chemistry).
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Figures
Figure 2 ORTEP diagram of 2 (top left), 3 (top right), 4 (bottom left) and 5 (bottom right). Thermal ellipsoids are depicted at 50% probability; hydrogen atoms and iPr groups have been omitted for clarity. Selected distances (Å) and angles (°) for 2: U–Ct1 1.9129(4) {1.9150(4)}, U–Ct2 2.4706(4) {2.4772(4)}, Ct1–U–Ct2 161.09(2) {159.83(2)}. Selected distances (Å) and angles (°) for 3: U–Ct1 1.92263(18), U–Ct2 2.48047(18), Ct1–U–Ct2 167.042(10). Selected distances (Å) and angles (°) 
Figure 3 ORTEP diagram of 6 (left) and 7 (right). Thermal ellipsoids are depicted at 50% probability; hydrogen atoms and iPr groups have been omitted for clarity. Selected distances (Å) and angles (°) for 6: U–Ct1 1.907(3) {1.901(3)}, U–Ct2 2.459(4) {2.459(4)}, Ct1–U–Ct2 154.61(11) {153.90(11)}. Selected distances (Å) and angles (°) for 7: U–Ct1 1.9177(18) {1.9057(15)}, U–Ct2 2.460(3) {2.4600(19)}, Ct1–U–Ct2 154.29(8) {152.27(7)}. Numbers in brackets represent values from the second independent molecule in the asymmetric unit. 
Figure 5 ORTEP diagram of 9 (thermal ellipsoids at 50% probability; hydrogen atoms and iPr groups have been omitted for clarity). There is 50:50 Me/H occupancy at the C16 position. Selected distances (Å) and angles (°): U–Ct1 1.9475(5), U–Ct2 2.496(5), Ct1–U–Ct2 141.8(1), U–O1 2.472(3), O1–C1 1.259(5), C1–C1' 1.472(9), C1–C1'' 1.442(9), C1–C1'–C1'' 90.0, U–C15 2.758(5), U–C16 2.730(5), U–C17 2.820(5). ![Table 1 Comparison of the G-parameter with the observed reactivity for [U(COTTIPS2)(CpR)] complexes. Values in italics represent those obtained from [U(COTTIPS2)(CpR)(THF)] complexes.](/figures/table-1-comparison-of-the-g-parameter-with-the-observed-88iwld58.png)
Table 1 Comparison of the G-parameter with the observed reactivity for [U(COTTIPS2)(CpR)] complexes. Values in italics represent those obtained from [U(COTTIPS2)(CpR)(THF)] complexes. 
Figure 6 ORTEP diagram of 12 (thermal ellipsoids at 50% probability; hydrogen atoms and iPr groups have been omitted for clarity). Selected distances (Å) and angles (°): U1–Ct1 1.9071(5), U1–Ct2 2.4651(5), U2–Ct3 1.9627(5), U2–Ct4 2.5021(5), Ct1–U1–Ct2 136.55(2), Ct3–U2–Ct4 136.85(2), Ct1–U1–U2–Ct3 77.6564(6), Ct2–U1–U2–Ct4 71.4376(5). 
Figure 4 ORTEP diagram of 8 (thermal ellipsoids at 50% probability; hydrogen atoms and iPr groups have been omitted for clarity). Selected distances (Å) and angles (°): U1–Ct1 1.9708(2), U2–Ct2 2.4932(2), U2–Ct3 1.9732(2), U2–Ct4 2.4959(2), Ct1–U1–Ct2 135.327(9), Ct3–U2–Ct4 136.724(10), U–O1 2.117(5), U–O1 2.110(4), Ct1–U1–U2–Ct3 108.549(2), Ct2–U1–U2–Ct4 136.2508(16).
![Table 1 Comparison of the G-parameter with the observed reactivity for [U(COTTIPS2)(CpR)] complexes. Values in italics represent those obtained from [U(COTTIPS2)(CpR)(THF)] complexes.](/figures/table-1-comparison-of-the-g-parameter-with-the-observed-88iwld58.webp)
Citations
Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2018
TL;DR: In 2018, a review of the progress in organo-f-element chemistry was published as discussed by the authors, which summarizes the progress made in organometaller chemistry during the year 2018.
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Small molecule activation by multimetallic uranium complexes supported by siloxide ligands
TL;DR: The ability of the tris-tert-butoxysiloxide ligands to trap alkali ions in these nitride or oxide complexes leads to unprecedented ligand based and metal based reduction and functionalization of N2, CO, CO2 and H2.
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Linear versus Bent Uranium(II) Metallocenes─A Local Vibrational Mode Study.
TL;DR: In this paper , the intrinsic strength of the U-ring interactions in 22 U(II) metallocenes with a novel bond strength measure based on local vibrational mode analysis was investigated.
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Reduction of CO2 and CS2 with Uranium(III) Metallocene Aryloxides
Abstract: : The reactivity of two metallocene aryloxide U(III) complexes, [(C 5 Me 5 ) 2 U(O-R)], R = 4-t BuC 6 H 4 , 1 ; R = 2,6-t Bu 2 - 4-CH 3 C 6 H 2 (BHT), 3 , with CO 2 and CS 2 has been investigated. The reaction of 1 with CO 2 produces a bridging oxo complex with loss of CO, [{(C 5 Me 5 ) 2 (4-t BuC 6 H 4 -O)U} 2 ( µ 2 -O)], 4 , while 3 with CO 2 results in reductive disproportionation to form the bridging carbonate species, [{(C 5 Me 5 ) 2 (BHT)U} 2 ( µ 2 - κ 2 : η 1 -CO 3 )], 5 . The difference in reactivity can be attributed by the steric properties of the ligand since reaction of 2 with an oxo-delivering agent yields the U(V) terminal oxo complex, [(C 5 Me 5 ) 2 (BHT)U=O], 6 . Reduction of CS 2 to form a bridging (CS 2 ) 2-ligand, [{(C 5 Me 5 ) 2 ( t BuC 6 H 4 -O)U} 2 ( µ 2 -CS 2 )], 7 , is observed with 1 , while reaction of 3 with CS 2 also produces a bridging (CS 2 ) 2-reduced ligand complex, followed by C-H bond activation of a methyl group from one (C 5 Me 5 ) 1-ring, [(C 5 Me 5 ) 2 (BHT)U{ µ 2 -C(H)S 2 }U(C 5 Me 4 CH 2 )(C 5 Me 5 )(BHT)], 8 . All compounds
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Replacing Trimethylsilyl with Triisopropylsilyl Provides Crystalline (C5H4SiR3)3Th Complexes of Th(III) and Th(II)
Joseph Q. Nguyen,Lauren M Anderson-Sanchez,William N. G. Moore,Joseph W. Ziller,Filipp Furche,William J. Evans +5 more
TL;DR: Replacing trimethylsilyl with triisopropylsilyl in cyclopentadienyl ligands enables the synthesis of crystalline thorium complexes, including Th(III) and Th(II) species, which were previously inaccessible due to instability, highlighting the importance of steric factors in their isolation.
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