Exploring Spin-Orbit Effects in a [Cu6Tl]+ Nanocluster Featuring an Uncommon Tl-H Interaction.

Reaction of [CuH(PPh3)]6 with 1 equiv. of Tl(OTf) results in formation of [Cu6TlH6(PPh3)6][OTf] ([1]OTf]), which can be isolated in good yields. Variable-temperature 1H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl-H orbital interaction. According to DFT, the 1H chemical shift of the Tl-adjacent hydride ligands of [1]+ includes 7.7 ppm of deshielding due to spin-orbit effects from the heavy Tl atom. This study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl-H interaction.

Quantifying Actinide-Carbon Bond Covalency in a Uranyl-Aryl Complex Utilizing Solution 13C NMR Spectroscopy.

Reaction of [UO2Cl2(THF)2]2 with in situ generated LiFmes (FmesH = 1,3,5-(CF3)3C6H3) in Et2O resulted in the formation of the uranyl aryl complexes [Li(THF)3][UO2(Fmes)3] ([Li(THF)3][1]) and [Li(Et2O)3(THF)][UO2(Fmes)3] ([Li(Et2O)3(THF)][1]) in good to moderate yields after crystallization from hexanes and Et2O, respectively. Both complexes were characterized by X-ray crystallography and NMR spectroscopy. DFT calculations reveal that the Cispo resonance in [1]- exhibits a deshielding of 51 ppm from spin-orbit coupling effects originating at uranium, which indicates an appreciable covalency in the U-C bonding interaction.

Dimerization and ring-opening in bis(diisopropylamino)cyclopropenylidene (BAC) mediated by [U(NR2)3(CCPh)] (R = SiMe3).

Addition of 2 equiv. of bis(diisopropylamino)cyclopropenylidene (BAC) to [U(NR2)3(CCPh)] (1, R = SiMe3), in Et2O, results in formation of [cyclo-N(iPr)C(Me)2CH(NiPr2)C{CHC3(NiPr2)2}][U(NR2)2(N(SiMe3)SiMe2CH2)(CCPh)] (2) in moderate isolated yield. Complex 2 is the result of coupling and protonation of two BAC molecules, where complex 1 contributes the required proton. It was characterized by NMR spectroscopy and X-ray crystallography and represents a new mode of reactivity of the cyclopropenylidene fragment.

Photolytic C-Diazeniumdiolate Disassembly in the ß-Diketiminate Complexes [MeLM(O2N2CPh3)] (M = Fe, Co, Cu).

The reaction of [K(18-crown-6)][O2N2CPh3] with [MeLCo(µ-Br)2Li(OEt2)] (MeL = {(2,6-iPr2C6H3)NC(Me)}2CH) generates the trityl diazeniumdiolate complex, [MeLCo(O2N2CPh3)] (1), in moderate yield. Similar metathesis reactions result in the formation of the Fe and Cu analogues, [MeLM(O2N2CPh3)] (Fe, 2; Cu, 3), which can also be isolated in moderate yields. Complexes 1-3 were characterized by ultraviolet-visible (UV-vis) spectroscopy, and their solid-state structures were determined by X-ray crystallography. These complexes were further characterized via 1H NMR spectroscopy (in the case of 1 and 2) or EPR spectroscopy (in the case of 3). Irradiation of complexes 1 and 2 with 371 nm light generates the known dinitrosyl complexes, [MeLM(NO)2] (M = Co, 4; Fe, 5), along with Ph3CH and 9-phenylfluorene. We propose that 4 and 5 are formed via the putative hyponitrite intermediates, [MeLM(κ2-O,O-ONNO)], which are formed by photoinduced homolysis of the C-N bond of the [O2N2CPh3] ligand. In contrast, irradiation of complex 3 with 371 nm light, in the presence of 1 equiv of PPh3, led to the formation of the Cu(I) complexes, [MeLCu(PPh3)], [(ArNCMeC(NO)CMeNAr)Cu(PPh3)] (6), and [(ArNCMeC(NO)CMeNAr)Cu]2 (7), of which the latter two are products of γ-nitrosation of the ß-diketiminiate ligand. Also formed in this transformation are Ph3CN(H)OCPh3, Ph3PO, and N2O, along with trace amounts of NO.

Measuring Metal-Metal Communication in a Series of Ketimide-Bridged [Fe2]6+ Complexes.

Reaction of Fe(acac)3 with 3 equiv of Li[N═C(R)Ph] (R = Ph, tBu) results in the formation of the [Fe2]6+ complexes, [Fe2(µ-N═C(R)Ph)2(N═C(R)Ph)4] (R = Ph, 1; tBu, 2), in low to moderate yields. Reaction of FeCl2 with 6 equiv of Li(N═C13H8) (HN═C13H8 = 9-fluorenone imine) results in the formation of [Li(THF)2]2[Fe(N═C13H8)4] (3) in good yield. Subsequent oxidation of 3 with ca. 0.8 equiv of I2 generates the [Fe2]6+ complex, [Fe2(µ-N═C13H8)2(N═C13H8)4] (4), along with free fluorenyl ketazine. Complexes 1, 2, and 4 were characterized by 1H NMR spectroscopy, X-ray crystallography, 57Fe Mössbauer spectroscopy, and SQUID magnetometry. The Fe-Fe distances in 1, 2, and 4 range from 2.803(7) to 2.925(1) Å, indicating that no direct Fe-Fe interaction is present in these complexes. The 57Fe Mössbauer spectra for complexes 1, 2, and 4 are all consistent with the presence of symmetry-equivalent high-spin Fe3+ centers. Finally, all three complexes exhibit a similar degree of antiferromagnetic coupling between the metal centers (J = -26 to -30 cm-1), as ascertained by SQUID magnetometry.

Evaluating f-Orbital Participation in the UV═E Multiple Bonds of [U(E)(NR2)3] (E = O, NSiMe3, NAd; R = SiMe3).

The reaction of 1 equiv of 1-azidoadamantane with [UIII(NR2)3] (R = SiMe3) in Et2O results in the formation of [UV(NR2)3(NAd)] (1, Ad = 1-adamantyl) in good yields. The electronic structure of 1, as well as those of the related U(V) complexes, [UV(NR2)3(NSiMe3)] (2) and [UV(NR2)3(O)] (3), were analyzed with EPR spectroscopy, SQUID magnetometry, NIR-visible spectroscopy, and crystal field modeling. This analysis revealed that, within this series of complexes, the steric bulk of the E2- (E═O, NR) ligand is the most important factor in determining the electronic structure. In particular, the increasing steric bulk of this ligand, on moving from O2- to [NAd]2-, results in increasing U═E distances and E-U-Namide angles. These changes have two principal effects on the resulting electronic structure: (1) the increasing U═E distances decreases the energy of the fσ orbital, which is primarily σ* with respect to the U═E bond, and (2) the increasing E-U-Namide angles increases the energy of fδ, due to increasing antibonding interactions with the amide ligands. As a result of the latter change, the electronic ground state for complexes 1 and 2 is primarily fφ in character, whereas the ground state for complex 3 is primarily fδ.

NO and N2O Release from the Trityl Diazeniumdiolate Complexes [M(O2N2CPh3)3]- (M = Fe, Co).

Reaction of MBr2 with 3 equiv of [K(18-crown-6)][O2N2CPh3] generates the trityl diazeniumdiolate complexes [K(18-crown-6)][M(O2N2CPh3)3] (M = Co, 2; Fe, 3) in good yields. Irradiation of 2 and 3 using 371 nm light led to NO formation in 10 and 1% yields (calculated assuming a maximum of 6 equiv of NO produced per complex), respectively. N2O was also formed during the photolysis of 2, in 63% yield, whereas photolysis of 3 led to the formation of N2O, as well as Ph3CN(H)OCPh3, in 37 and 5% yields, respectively. These products are indicative of diazeniumdiolate fragmentation via both C-N and N-N bond cleavage pathways. In contrast, oxidation of complexes 2 and 3 with 1.2 equiv of [Ag(MeCN)4][PF6] led to N2O formation but no NO formation, suggesting that diazeniumdiolate fragmentation occurs exclusively via C-N bond cleavage under these conditions. While the photolytic yields of NO are modest, they represent a 10- to 100-fold increase compared to the previously reported Zn congener, suggesting that the presence of a redox-active metal center favors NO formation upon trityl diazeniumdiolate fragmentation.

Photolytic or Oxidative Fragmentation of Trityl Diazeniumdiolate (O2N2CPh3-): Evidence for Both C-N and N-N Bond Cleavage.

Exposure of [K(18-crown-6)(THF)2][CPh3] (THF = tetrahydrofuran; Ph = phenyl) to an atmosphere of nitric oxide (NO) cleanly generates [K(18-crown-6)][O2N2CPh3] (1) in excellent yields. A subsequent reaction of [ZnCl2(THF)2] with 3 equiv of 1 affords the C-diazeniumdiolate complex [K(18-crown-6)][Zn(O2N2CPh3)3] (2). Both 1 and 2 were characterized by 1H and 13C{1H} NMR spectroscopy, and their structures were confirmed by X-ray crystallography. Photolysis of 2 using 371 nm light resulted in the formation of three trityl-containing products, namely, Ph3CH, 9-phenylfluorene, and Ph3CN(H)OCPh3 (3). In addition, we detected nitrous oxide (N2O), as well as small amounts of NO in the reaction mixture. In contrast, oxidation of 2 with 1.2 equiv of [Ag(MeCN)4][PF6] resulted in the formation of O(CPh3)2 as the major trityl-containing product; N2O was also detected in the reaction mixture, but NO was not apparently formed in this case. The observation of these fragmentation products indicates that the [O2N2CPh3]- ligand is susceptible to both C-N bond and N-N bond cleavage. Moreover, the different product distributions suggest that [O2N2CPh3]- is susceptible to different modes of fragmentation.

Assessing the 4f Orbital Participation in the Ln-C Bonds of [Li(THF)4][Ln(C6Cl5)4] (Ln = La, Ce).

The reaction of [Ln(NO3)3(THF)4] (Ln = La, Ce) with 4 equiv of LiC6Cl5 in Et2O resulted in the formation of the homoleptic lanthanide-aryl "ate" complexes [Li(THF)4][La(C6Cl5)4] ([Li][1]) and [Li(THF)4][Ce(C6Cl5)4] ([Li][2]). These complexes represent the first isolated homoleptic perchlorophenyl complexes for the lanthanides. In the solid state, both [Li][1] and [Li][2] exhibit octa-coordinate lanthanide centers, with four Ln-C σ-bonds and four Cl → Ln dative interactions involving the ortho-Cl atoms of the C6Cl5 ligands. Despite this apparent steric saturation, both [Li][1] and [Li][2] are highly temperature sensitive and quickly decompose in solution at room temperature. Density functional calculations show that the Ln-Cipso donation bonds feature only weak 4f participation (e.g., ∼1% 4f weight for [1]-). Nonetheless, the 13C chemical shift of the Cipso nuclei of [1]- includes ca. 8 ppm of deshielding from the spin-orbit interaction due to the participation of the 4f (and 5d) orbitals in the La-C bonds.

Structural and Spectroscopic Characterization of a Zinc-Bound N-Oxyphthalimide Radical.

Thermolysis of a 1:1:1 mixture of MeLH (MeL = {(2,6-iPr2C6H3)NC(Me)}2CH), N-hydroxyphthalimide (HOPth), and diethylzinc in toluene at 77 °C provided [MeLZn(OPth)] (1) in good yield after workup. The subsequent reduction of 1 with 1.3 equiv of KC8 and 1 equiv of 2.2.2-cryptand, in tetrahydrofuran, provided [K(2.2.2-cryptand)][MeLZn(OPth)] (2) in 74% yield after workup. Characterization of 2 via X-ray crystallography and electron paramagnetic resonance spectroscopy reveals the presence of an S = 1/2 radical on the N-oxyphthalimide ligand. Importantly, these data represent the first structural and spectroscopic confirmation of the redox activity of a metal-bound N-oxyphthalimide fragment, expanding the range of structurally characterized redox-active ligands.

[Ni30S16(PEt3)11]: an open-shell nickel sulfide nanocluster with a "metal-like" core.

Reaction of [Ni(1,5-cod)2] (30 equiv.) with PEt3 (46 equiv.) and S8 (1.9 equiv.) in toluene, followed by heating at 115 °C for 16 h, results in the formation of the atomically precise nanocluster (APNC), [Ni30S16(PEt3)11] (1), in 14% isolated yield. Complex 1 represents the largest open-shell Ni APNC yet isolated. In the solid state, 1 features a compact "metal-like" core indicative of a high degree of Ni-Ni bonding. Additionally, SQUID magnetometry suggests that 1 possesses a manifold of closely-spaced electronic states near the HOMO-LUMO gap. In situ monitoring by ESI-MS and 31P{1H} NMR spectroscopy reveal that 1 forms via the intermediacy of smaller APNCs, including [Ni8S5(PEt3)7] and [Ni26S14(PEt3)10] (2). The latter APNC was also characterized by X-ray crystallography and features a nearly identical core structure to that found in 1. This work demonstrates that large APNCs with a high degree of metal-metal bonding are isolable for nickel, and not just the noble metals.

Metal-Metal-Bonded Fe4 Clusters with Slow Magnetic Relaxation.

Reaction of FeBr2 with Li(N═CtBu2) (0.5 equiv) and Zn0 (2 equiv) results in the formation of the formally mixed-valent cluster [Fe4Br2(N═CtBu2)4] (1) in moderate yield. The subsequent reaction of 1 with Na(N═CtBu2) results in formation of [Fe4Br(N═CtBu2)5] (2), also in moderate yield. Both 1 and 2 were characterized by zero-field 57Fe Mössbauer spectroscopy, X-ray crystallography, and superconducting quantum interference device magnetometry. Their tetrahedral [Fe4]6+ cores feature short Fe-Fe interactions (ca. 2.50 Å). Additionally, both 1 and 2 display S = 7 ground states at room temperature and slow magnetic relaxation with zero-field relaxation barriers of Ueff = 14.7(4) and 15.6(7) cm-1, respectively. Moreover, AC magnetic susceptibility measurements were well modeled by assuming an Orbach relaxation process.

Ring-opening of a thorium cyclopropenyl complex generates a transient thorium-bound carbene.

The reaction of [Cp3ThCl] with in situ generated 1-lithium-3,3-diphenylcyclopropene results in the formation of [Cp3Th(3,3-diphenylcyclopropenyl)] (1), in good yields. Thermolysis of 1 results in isomerization to the ring-opened product, [Cp3Th(3-phenyl-1H-inden-1-yl)] (3) via a hypothesized carbene intermediate. This transformation represents a new mode of reactivity of 3,3-diphenylcyclopropene with the actinides, improving our ability to use this reagent as a carbene source. A combined DFT and 13C{1H} NMR analysis of 1 shows a spin-orbit induced downfield shift at Cα due to participation of the 5f orbitals in the Th-C bond.

Selective electrochemical capture and release of uranyl from aqueous alkali, lanthanide, and actinide mixtures using redox-switchable carboranes.

We report the selective electrochemical biphasic capture of the uranyl cation (UO2 2+) from mixed-metal alkali (Cs+), lanthanide (Nd3+, Sm3+), and actinide (Th4+, UO2 2+) aqueous solutions to an organic, 1,2-dichloroethane (DCE), phase using the ortho-substituted nido-carborane anion, [1,2-(Ph2PO)2-1,2-C2B10H10]2- (POCb2-). The reduced POCb2- is generated by electrochemical reduction of the closo-carborane, POCb, prior to mixing with the aqueous mixed-metal solution. Subsequent UO2 2+ release from the captured product, [UO2(POCb)2]2-, was performed by galvanostatic bulk electrolysis of the DCE phase and back-extraction of UO2 2+ to a fresh aqueous phase. The selective capture and release of UO2 2+ was confirmed by combined ICP-OES and NMR spectral analyses of the aqueous and organic phases, respectively, against the newly synthesized nido-carborane complexes, [[CoCp*2][Cs(POCb)]]2, [CoCp*2]3[Nd(POCb)3], [CoCp*2]3[Sm(POCb)3], and [CoCp*2]2[Th(POCb)3].

Synthesis and electronic structure analysis of the actinide allenylidenes, [{(NR2)3}An(CCCPh2)]- (An = U, Th; R = SiMe3).

The reaction of [AnCl(NR2)3] (An = U, Th, R = SiMe3) with in situ generated lithium-3,3-diphenylcyclopropene results in the formation of [{(NR2)3}An(CH[double bond, length as m-dash]C[double bond, length as m-dash]CPh2)] (An = U, 1; Th, 2) in good yields after work-up. Deprotonation of 1 or 2 with LDA/2.2.2-cryptand results in formation of the anionic allenylidenes, [Li(2.2.2-cryptand)][{(NR2)3}An(CCCPh2)] (An = U, 3; Th, 4). The calculated 13C NMR chemical shifts of the Cα, Cß, and Cγ nuclei in 2 and 4 nicely reproduce the experimentally assigned order, and exhibit a characteristic spin-orbit induced downfield shift at Cα due to involvement of the 5f orbitals in the Th-C bonds. Additionally, the bonding analyses for 3 and 4 show a delocalized multi-center character of the ligand π orbitals involving the actinide. While a single-triple-single-bond resonance structure (e.g., An-C[triple bond, length as m-dash]C-CPh2) predominates, the An[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CPh2 resonance form contributes, as well, more so for 3 than for 4.

[Ni23Se12(PEt3)13] Revisited: Isolation and Characterization of [Ni23Se12Cl3(PEt3)10].

The reaction of [Ni(1,5-COD)2] (1.0 equiv), PEt3 (0.04 equiv), SePEt3 (0.52 equiv), and [NiCl2(PEt3)2] (0.07 equiv) in a mixture of toluene and THF results in the formation of [Ni23Se12Cl3(PEt3)10] (1), which can be isolated in moderate yield after workup. Complex 1 was characterized by NMR spectroscopy, ESI-MS, and X-ray crystallography. This open-shell nanocluster features a central [Ni13]7+ anticuboctahedral kernel, which is encapsulated by a [Ni10(µ-Se)9Cl3]- shell, along with ten PEt3 ligands and three (µ4-Se)2- ligands. On the basis of our spectroscopic and crystallographic analysis, coupled with in situ spectroscopic monitoring, we believe that the previously reported nanocluster, [Ni23Se12(PEt3)13], is actually better formulated as [Ni23Se12Cl3(PEt3)10].

Synthesis of Parent Acetylide and Dicarbide Complexes of Thorium and Uranium and an Examination of Their Electronic Structures.

The reaction of [AnCl(NR2)3] (An = U or Th; R = SiMe3) with NaCCH and tetramethylethylenediamine (TMEDA) results in the formation of [An(C≡CH)(NR2)3] (1, An = U; 2, An = Th), which can be isolated in good yields after workup. Similarly, the reaction of 3 equiv of NaCCH and TMEDA with [AnCl(NR2)3] results in the formation of [Na(TMEDA)][An(C≡CH)2(NR2)3] (4, An = U; 5, An = Th), which can be isolated in fair yields after workup. The reaction of 1 with 2 equiv of KC8 and 1 equiv of 2.2.2-cryptand in tetrahydrofuran results in formation of the uranium(III) acetylide complex [K(2.2.2-cryptand)][U(C≡CH)(NR2)3] (3). Thermolysis of 1 or 2 results in formation of the bimetallic dicarbide complexes [{An(NR2)3}2(µ,η1:η1-C2)] (6, An = U; 7, An = Th), whereas the reaction of 1 with [Th{N(R)(SiMe2CH2)}(NR2)2] results in the formation of [U(NR2)3(µ,η1:η1-C2)Th(NR2)3] (8). The 13C NMR chemical shifts of the α-acetylide carbon atoms in 2, 5, and 7 exhibit a characteristic spin-orbit-induced downfield shift, due to participation of the 5f orbitals in the Th-C bonds. Magnetism measurements demonstrate that 6 displays weak ferromagnetic coupling between the uranium(IV) centers (J = 1.78 cm-1).

[Ni8(CNtBu)12][Cl]: A nickel isocyanide nanocluster with a folded nanosheet structure.

The reaction of 1.75 equiv of tBuNC with Ni(1,5-COD)2, followed by crystallization from benzene/pentane, resulted in the isolation of [Ni8(CNtBu)12][Cl] (2) in low yields. Similarly, the reaction of Ni(1,5-COD)2 with 0.6 equiv of [Ni(CNtBu)4], followed by addition of 0.08 equiv of I2, resulted in the formation of [Ni8(CNtBu)12][I] (3), which could be isolated in 52% yield after work-up. Both 2 and 3 adopt folded nanosheet structures in the solid state, characterized by two symmetry-related planar Ni4 arrays, six terminally bound tBuNC ligands, and six tBuNC ligands that adopt bridging coordination modes. The metrical parameters of the six bridging tBuNC ligands suggest that they have been reduced to their [tBuNC]2- form. In contrast to the nanosheet structures observed for 2 and 3, gas phase Ni8 is predicted to feature a compact bisdisphenoid ground state structure. The strikingly different structural outcomes reveal the profound structural changes that can occur upon addition of ligands to bare metal clusters. Ultimately, the characterization of 2 and 3 will enable more accurate structural predictions of ligand-protected nanoclusters in the future.