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Hydrogenolysis of the half-sandwich penta-arylcycopentadienyl-supported rare-earth metal dibenzyl complexes [(CpAr5)Ln(p-CH2-C6H4-Me)2(THF)] (CpAr5 = C5Ar5, Ar = 3,5-iPr2-C6H3; Ln = Sc, La) afforded a bimetallic scandium complex [(CpAr5)Sc(H)(μ-OC4H9)]2 (2) with two terminal hydrido ligands, and a double-sandwich bimetallic lanthanum hydride complex [(CpAr5)La(μ-H)]2 (4) bearing the reduced CpAr5 ligand. DFT calculations were conducted to elucidate the reaction profiles. [ABSTRACT FROM AUTHOR]

Hydrogenolysis of alkyl‐substituted cyclopentadienyl (CpR) ligated thorium tribenzyl complexes [(CpR)Th(p‐CH2‐C6H4‐Me)3] (1–6) afforded the first examples of molecular thorium trihydrido complexes [(CpR)Th(μ‐H)3]n (CpR=C5H2(tBu)3 or C5H2(SiMe3)3, n=5; C5Me4SiMe3, n=6; C5Me5, n=7; C5Me4H, n=8; 7–10 and 12) and [(Cp#)12Th13H40] (Cp#=C5H4SiMe3; 13). The nuclearity of the metal hydride clusters depends on the steric profile of the cyclopentadienyl ligands. The hydrogenolysis intermediate, tetra‐nuclear octahydrido thorium dibenzylidene complex [(Cpttt)Th(μ‐H)2]4(μ‐p‐CH‐C6H4‐Me)2 (Cpttt=C5H2(tBu)3) (11) was also isolated. All of the complexes were characterized by NMR spectroscopy and single‐crystal X‐ray analysis. Hydride positions in [(CpMe4)Th(μ‐H)3]8 (CpMe4=C5Me4H) were further precisely confirmed by single‐crystal neutron diffraction. DFT calculations strengthen the experimental assignment of the hydride positions in the complexes 7 to 12. [ABSTRACT FROM AUTHOR]

Hydrogenolysis of alkyl‐substituted cyclopentadienyl (CpR) ligated thorium tribenzyl complexes [(CpR)Th(p‐CH2‐C6H4‐Me)3] (1–6) afforded the first examples of molecular thorium trihydrido complexes [(CpR)Th(μ‐H)3]n (CpR=C5H2(tBu)3 or C5H2(SiMe3)3, n=5; C5Me4SiMe3, n=6; C5Me5, n=7; C5Me4H, n=8; 7–10 and 12) and [(Cp#)12Th13H40] (Cp#=C5H4SiMe3; 13). The nuclearity of the metal hydride clusters depends on the steric profile of the cyclopentadienyl ligands. The hydrogenolysis intermediate, tetra‐nuclear octahydrido thorium dibenzylidene complex [(Cpttt)Th(μ‐H)2]4(μ‐p‐CH‐C6H4‐Me)2 (Cpttt=C5H2(tBu)3) (11) was also isolated. All of the complexes were characterized by NMR spectroscopy and single‐crystal X‐ray analysis. Hydride positions in [(CpMe4)Th(μ‐H)3]8 (CpMe4=C5Me4H) were further precisely confirmed by single‐crystal neutron diffraction. DFT calculations strengthen the experimental assignment of the hydride positions in the complexes 7 to 12. [ABSTRACT FROM AUTHOR]

The monomeric actinide dihydrido complex [(CpAr*)(Cp*)ThH2(THF)] (2) bearing the super-bulky penta-arylcyclopentadienyl (CpAr* = C5Ar*5, Ar* = 3,5-tBu2-C6H3) and pentamethylcyclopentadienyl (Cp* = C5Me5) ligands was obtained for the first time. Complex 2 underwent unique Th–H addition reactions with various unsaturated compounds to afford the corresponding five-membered metallacycles, including the first example of actinide metallacyclopentyne [(CpAr*)(Cp*)Th(PhCH–C≡C–CHPh)] (4). [ABSTRACT FROM AUTHOR]

Abstract: The preferential substitution of oxo ligands over alkyl ones of rare‐earth complexes is commonly considered as “impossible” due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare‐earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln‐oxo bond, but also protect the highly reactive Ln‐alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non‐redox rare‐earth‐mediated oxygen atom transfer from ketones to CS2 and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare‐earth oxo complexes. [ABSTRACT FROM AUTHOR]

Abstract: The preferential substitution of oxo ligands over alkyl ones of rare‐earth complexes is commonly considered as “impossible” due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare‐earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln‐oxo bond, but also protect the highly reactive Ln‐alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non‐redox rare‐earth‐mediated oxygen atom transfer from ketones to CS2 and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare‐earth oxo complexes. [ABSTRACT FROM AUTHOR]

Lu[CH(SiMe3)2]3 reacts with [SiO2-700] to give [(≡SiO)Lu[CH(SiMe3)2]2] and CH2(SiMe3)2. [(≡SiO)Lu[CH(SiMe3)2]2] is characterized by solid-state NMR and EXAFS spectroscopy, which show that secondary Lu•••C and Lu•••O interactions, involving a γ-CH3 and a siloxane bridge, are present. From X-ray crystallographic analysis, the molecular analogues Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 0-2) also have secondary Lu•••C interactions. The 1H NMR spectrum of Lu[CH(SiMe3)2]3 shows that the -SiMe3 groups are equivalent to -125 °C and inequivalent below that temperature, ΔG‡(Tc = 148 K) = 7.1 kcal mol-1. Both -SiMe3 groups in Lu[CH(SiMe3)2]3 have 1JCH = 117 ± 1 Hz at -140 °C. The solid-state 13C CPMAS NMR spectrum at 20 °C shows three chemically inequivalent resonances in the area ratio of 4:1:1 (12:3:3); the J-resolved spectra for each resonance give 1JCH = 117 ± 2 Hz. The 29Si CPMAS NMR spectrum shows two chemically inequivalent resonances with different values of chemical shift anisotropy. Similar observations are obtained for Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 1 and 2). The spectroscopic data point to short Lu•••Cγ contacts corresponding to 3c-2e Lu•••Cγ-Siβ interactions, which are supported by DFT calculations. Calculated natural bond orbital (NBO) charges show that Cγ carries a negative charge, while Lu, Hγ, and Siβ carry positive charges; as the number of O-based ligands increases so does the positive charge at Lu, which in turns shortens the Lu•••Cγ distance. The change in NBO charges and the resulting changes in the spectroscopic and crystallographic properties show how ligands and surface-support sites rearrange to accommodate these changes, consistent with Pauling's electroneutrality concept. [ABSTRACT FROM AUTHOR]

Introduction of four tBu groups into a carbazol-ylframework leads to switching of the metal–ligand bonding inthe Ln(II) and Ca complexes from σ to π. Complexes [(tBu4Carb)2Ln] (Ln = Sm, Eu, Yb, Ca)are amido analogues of metallocenes, which adopt the sandwich structureswith parallel disposition of the aromatic ligands and strong contributionof η3-mode into η5metal–ligandbonding. The DFT calculations demonstratedthat the geometry is due to steric effects (presence of the bulky tBu groups) as well as the maximization of the overlap betweenthe Sm 4f orbital and the π-type nitrogen lone pairof the carbazol-yl ligand. Coordination of DME to the metal centersin [(tBu4Carb)2M] (M = Sm,Yb) results in the heterolytic dissociation of the metal–ligandπ-bond and the formation of ionic complexes [tBu4Carb–]2[Ln2+(DME)n]. [ABSTRACT FROM AUTHOR]