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A novel Ta/Os heterobimetallic complex, [Ta(CH2tBu)3(μ-H)3OsCp*], 2, is prepared by protonolysis of Ta(CHtBu)(CH2tBu)3 with Cp*OsH5. Treatment of 2 and its iridium analogue [Ta(CH2tBu)3(μ-H)2IrCp*], 1, with CO2 under mild conditions reveal the efficient cleavage of CO2, driven by the formation of a tantalum oxo species in conjunction with CO transfer to the osmium or iridium fragments, to form Cp*Ir(CO)H2 and Cp*Os(CO)H3, respectively. This bimetallic reactivity diverges from more classical CO2 insertion into metal-X (X = metal, hydride, alkyl) bonds.

Transition metal multimetallic complexes have seen intense study due to their unique bonding and potential for cooperative reactivity, but actinide-transition metal (An-TM) species are far less understood. We have synthesized uranium- and thorium-osmium heterometallic polyhydride complexes in order to study An-Os bonding and investigate the reactivity of An-Os interactions. Computational studies suggest the presence of a significant bonding interaction between the actinide center and the four coordinated osmium centers supported by bridging hydrides. Upon photolysis, these complexes undergo intramolecular C-H activation with the formation of an Os-Os bond, while the thorium complex may activate an additional C-H bond of the benzene solvent, resulting in a μ-η1,η1 phenyl ligand across one Th-Os interaction.

Reaction of the potassium pentamethylcyclopentadienyl iridate tris-hydride K[IrCp*H3] with UCl4 and ThCl4(DME)2 led to the complete replacement of the halide ligands to generate multimetallic complexes U{(μ-H)3IrCp*}4 (1) and Th{[(μ-H2)(H)IrCp*]2[(μ-H)3IrCp*]2} (2), respectively. These analogues feature a significant discrepancy in hydride bonding modes; 1 contains twelve bridging hydrides while 2 contains ten bridging hydrides and two terminal, Ir-bound hydrides. Use of a U(iii) starting material, UI3(1,4-dioxane)1.5, resulted in the octanuclear complex {U[(μ2-H3)IrCp*]2[(μ3-H2)IrCp*]}2 (3). Computational studies indicate significant bonding character between U/Th and Ir in 1 and 2, with f-orbital involvement in the singly-occupied molecular orbitals of the uranium species 1. In addition, these studies attribute the variation in hydride bonding between 1 and 2 to differences in dispersion effects.

Two-electron reduction of the amidate-supported U(III) mono(arene) complex U(TDA)3 (2) with KC8 yields the anionic bis(arene) complex [K[2.2.2]cryptand][U(TDA)2] (3) (TDA = N-(2,6-di-isopropylphenyl)pivalamido). EPR spectroscopy, magnetic susceptibility measurements, and calculations using DFT as well as multireference CASSCF methods all provide strong evidence that the electronic structure of 3 is best represented as a 5f4 U(II) metal center bound to a monoreduced arene ligand. Reactivity studies show 3 reacts as a U(I) synthon by behaving as a two-electron reductant toward I2 to form the dinuclear U(III)-U(III) triiodide species [K[2.2.2]cryptand][(UI(TDA)2)2(μ-I)] (6) and as a three-electron reductant toward cycloheptatriene (CHT) to form the U(IV) complex [K[2.2.2]cryptand][U(η7-C7H7)(TDA)2(THF)] (7). The reaction of 3 with cyclooctatetraene (COT) generates a mixture of the U(III) anion [K[2.2.2]cryptand][U(TDA)4] (1-crypt) and U(COT)2, while the addition of COT to complex 2 instead yields the dinuclear U(IV)-U(IV) inverse sandwich complex [U(TDA)3]2(μ-η8:η3-C8H8) (8). Two-electron reduction of the homoleptic Th(IV) amidate complex Th(TDA)4 (4) with KC8 gives the mono(arene) complex [K[2.2.2]cryptand][Th(TDA)3(THF)] (5). The C-C bond lengths and torsion angles in the bound arene of 5 suggest a direduced arene bound to a Th(IV) metal center; this conclusion is supported by DFT calculations.

A novel Ta/Os heterobimetallic complex, [Ta(CH2tBu)3(μ-H)3OsCp*], 2, is prepared by protonolysis of Ta(CHtBu)(CH2tBu)3 with Cp*OsH5. Treatment of 2 and its iridium analogue [Ta(CH2tBu)3(μ-H)2IrCp*], 1, with CO2 under mild conditions reveal the efficient cleavage of CO2, driven by the formation of a tantalum oxo species in conjunction with CO transfer to the osmium or iridium fragments, to form Cp*Ir(CO)H2 and Cp*Os(CO)H3, respectively. This bimetallic reactivity diverges from more classical CO2 insertion into metal–X (X = metal, hydride, alkyl) bonds. [ABSTRACT FROM AUTHOR]

Two‐electron oxidative addition is one of the most important elementary reactions for d‐block transition metals but it is uncommon for f‐block elements. Here, we report the first examples of intermolecular oxidative addition of E−H (E=C, N) bonds to uranium(II) centers. The transient U(II) species was formed in‐situ by reducing a heterometallic cluster featuring U(IV)‐Pd(0) bonds with potassium‐graphite (KC8). Oxidative addition of C−H or N−H bonds to the U(II) centers was observed when this transient U(II) species was treated with benzene, carbazole or 1‐adamantylamine, respectively. The U(II) centers could also react with tetracene, biphenylene or N2O, leading to the formation of arene reduced U(IV) products and uranyl(VI) species via two‐ or four‐electron processes. This study demonstrates that the intermolecular two‐electron oxidative addition reactions are viable for actinide elements. [ABSTRACT FROM AUTHOR]

Polynuclear metal hydride clusters play important roles in various catalytic processes, with most of the reported polynuclear metal hydride clusters adopting a polyhedral three‐dimensional structure. Herein, we report the first example of a planar tetranuclear uranium hydride cluster [(CpCMe2CMe2Cp)U]4(μ2‐H)4(μ3‐H)4 (U4H8). It was synthesized by reacting an ansa‐bis(cyclopentadienyl) ligand‐supported uranium chloride precursor [(CpCMe2CMe2Cp)U]3(μ2‐Cl)3(μ3‐Cl)2 with NaHBEt3. The presence of hydrides in U4H8 was confirmed by NMR spectroscopy and its reactivity with phenol and carbon tetrachloride. DFT calculations also facilitated the determination of the hydrides' positions in U4H8, featuring four bridging μ2‐H ligands and four face‐capping μ3‐H ligands, with the four U centers arranged in a rhombic geometry. The U4H8 represents not only the first example of planar polynuclear actinide metal hydride cluster but also the uranium hydride cluster with the highest nuclearity reported to date. [ABSTRACT FROM AUTHOR]

We have re‐examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] (1, Cp=η5‐cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li (3) that is stable only below −40 °C. Full characterization of 3 (including single crystal X‐ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li (2). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so‐far unique behavior of the N2 ligand in 1. DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal‐coordinated N2 remains to be demonstrated. [ABSTRACT FROM AUTHOR]

We have re‐examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] (1, Cp=η5‐cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li (3) that is stable only below −40 °C. Full characterization of 3 (including single crystal X‐ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li (2). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so‐far unique behavior of the N2 ligand in 1. DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal‐coordinated N2 remains to be demonstrated. [ABSTRACT FROM AUTHOR]

Reduction of a range of amido‐ and aryloxy‐aluminum dihydride complexes, e.g. [AlH2(NR3){N(SiMe3)2}] (NR3=NMe3 or N‐methylpiperidine (NMP)), with β‐diketiminato dimagnesium(I) reagents, [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]−, Ar=mesityl (Mes) or 2,6‐xylyl (Xyl)), have afforded deep red mixed valence aluminum hydride cluster compounds, [Al6H8(NR3)2{Mg(ArNacnac)}4], which have an average Al oxidation state of +0.66, the lowest for any well‐defined aluminum hydride compound. In the solid‐state, the clusters are shown to have distorted octahedral Al6 cores, having zero‐valent Al axial sites and mono‐valent AlH2− equatorial units. Several novel by‐products were isolated from the reactions that gave the clusters, including the Mg−Al bonded magnesio‐aluminate complexes, [(ArNacnac)(Me3N)Mg−Al(μ‐H)3[{Mg(ArNacnac)}2(μ‐H)]]. Computational analyses of one aluminum hydride cluster revealed its Al6 core to be electronically delocalized, and to possess one unoccupied, and six occupied, skeletal molecular orbitals. [ABSTRACT FROM AUTHOR]

Reduction of a range of amido‐ and aryloxy‐aluminum dihydride complexes, e.g. [AlH2(NR3){N(SiMe3)2}] (NR3=NMe3 or N‐methylpiperidine (NMP)), with β‐diketiminato dimagnesium(I) reagents, [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]−, Ar=mesityl (Mes) or 2,6‐xylyl (Xyl)), have afforded deep red mixed valence aluminum hydride cluster compounds, [Al6H8(NR3)2{Mg(ArNacnac)}4], which have an average Al oxidation state of +0.66, the lowest for any well‐defined aluminum hydride compound. In the solid‐state, the clusters are shown to have distorted octahedral Al6 cores, having zero‐valent Al axial sites and mono‐valent AlH2− equatorial units. Several novel by‐products were isolated from the reactions that gave the clusters, including the Mg−Al bonded magnesio‐aluminate complexes, [(ArNacnac)(Me3N)Mg−Al(μ‐H)3[{Mg(ArNacnac)}2(μ‐H)]]. Computational analyses of one aluminum hydride cluster revealed its Al6 core to be electronically delocalized, and to possess one unoccupied, and six occupied, skeletal molecular orbitals. [ABSTRACT FROM AUTHOR]

This work reports the first catalyzed synthesis of d-block metalmetal bonded complexes. The treatment of terminal zinc hydrides [LZnH] [L = CH3C(2,6-iPr2C6H3N)CHC(CH3) (N(CH2)nCH2PR2); n = 1, 2; R = Ph, iPr] in the presence of 5 mol% Ni(CO)2(PPh3)2 afforded Zn(I)-Zn(I) bonded compounds [L2Zn2] in high isolated yields with concomitant elimination of dihydrogen. Stoichiometric reactions, kinetic studies and DFT calculations were conducted to elucidate the reaction mechanism. [ABSTRACT FROM AUTHOR]

RuNi nanoparticles (NP) were prepared by decomposition of [Ru(η4-C8H12)(η6-C8H10)] and [Ni(η4-C8H12)2] by H2 in the presence of polyvinylpyrrolidone (PVP) at 85 °C using several Ru/Ni ratios. The nanoparticles display a segregated structure in which Ni is on the surface, as ascertained by wide angle X-ray scattering (WAXS). The catalytic activity in the selective hydrogenation of furfural of these RuNi NP was correlated with the Ru content. High selectivity towards the partially hydrogenated product 2-(hydroxymethyl)furan (HF) was found when carrying out the reaction in tetrahydrofuran (THF). A different scenario was found when using a protic polar solvent, 1-propanol. Catalysts displaying Ru on the surface were able to hydrogenate the heteroaromatic ring, while those with Ni on the surface were highly selective towards the partially hydrogenated product. In addition, Ru surfaces were prone to catalyse the acetalization reaction in the presence of the alcoholic solvent, while the addition of Ni supressed this reactivity. Density functional theory (DFT) calculations performed on hydrogenated Ru nanoparticles (Ru55H70) show differences in the adsorption energies of several reagents, products, reaction intermediates, and solvents onto the Ru NP surface, which are in line with the experimental catalytic results. [ABSTRACT FROM AUTHOR]

We have re‐examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] (1, Cp=η5‐cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li (3) that is stable only below −40 °C. Full characterization of 3 (including single crystal X‐ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li (2). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so‐far unique behavior of the N2 ligand in 1. DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal‐coordinated N2 remains to be demonstrated. [ABSTRACT FROM AUTHOR]

We have re‐examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] (1, Cp=η5‐cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li (3) that is stable only below −40 °C. Full characterization of 3 (including single crystal X‐ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li (2). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so‐far unique behavior of the N2 ligand in 1. DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal‐coordinated N2 remains to be demonstrated. [ABSTRACT FROM AUTHOR]

Reduction of a range of amido‐ and aryloxy‐aluminum dihydride complexes, e.g. [AlH2(NR3){N(SiMe3)2}] (NR3=NMe3 or N‐methylpiperidine (NMP)), with β‐diketiminato dimagnesium(I) reagents, [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]−, Ar=mesityl (Mes) or 2,6‐xylyl (Xyl)), have afforded deep red mixed valence aluminum hydride cluster compounds, [Al6H8(NR3)2{Mg(ArNacnac)}4], which have an average Al oxidation state of +0.66, the lowest for any well‐defined aluminum hydride compound. In the solid‐state, the clusters are shown to have distorted octahedral Al6 cores, having zero‐valent Al axial sites and mono‐valent AlH2− equatorial units. Several novel by‐products were isolated from the reactions that gave the clusters, including the Mg−Al bonded magnesio‐aluminate complexes, [(ArNacnac)(Me3N)Mg−Al(μ‐H)3[{Mg(ArNacnac)}2(μ‐H)]]. Computational analyses of one aluminum hydride cluster revealed its Al6 core to be electronically delocalized, and to possess one unoccupied, and six occupied, skeletal molecular orbitals. [ABSTRACT FROM AUTHOR]

Reduction of a range of amido‐ and aryloxy‐aluminum dihydride complexes, e.g. [AlH2(NR3){N(SiMe3)2}] (NR3=NMe3 or N‐methylpiperidine (NMP)), with β‐diketiminato dimagnesium(I) reagents, [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]−, Ar=mesityl (Mes) or 2,6‐xylyl (Xyl)), have afforded deep red mixed valence aluminum hydride cluster compounds, [Al6H8(NR3)2{Mg(ArNacnac)}4], which have an average Al oxidation state of +0.66, the lowest for any well‐defined aluminum hydride compound. In the solid‐state, the clusters are shown to have distorted octahedral Al6 cores, having zero‐valent Al axial sites and mono‐valent AlH2− equatorial units. Several novel by‐products were isolated from the reactions that gave the clusters, including the Mg−Al bonded magnesio‐aluminate complexes, [(ArNacnac)(Me3N)Mg−Al(μ‐H)3[{Mg(ArNacnac)}2(μ‐H)]]. Computational analyses of one aluminum hydride cluster revealed its Al6 core to be electronically delocalized, and to possess one unoccupied, and six occupied, skeletal molecular orbitals. [ABSTRACT FROM AUTHOR]

Two-electron oxidative addition is one of the most important elementary reactions for d-block transition metals but it is uncommon for f-block elements. Here, we report the first examples of intermolecular oxidative addition of E-H (E=C, N) bonds to uranium(II) centers. The transient U(II) species was formed in-situ by reducing a heterometallic cluster featuring U(IV)-Pd(0) bonds with potassium-graphite (KC 8 ). Oxidative addition of C-H or N-H bonds to the U(II) centers was observed when this transient U(II) species was treated with benzene, carbazole or 1-adamantylamine, respectively. The U(II) centers could also react with tetracene, biphenylene or N 2 O, leading to the formation of arene reduced U(IV) products and uranyl(VI) species via two- or four-electron processes. This study demonstrates that the intermolecular two-electron oxidative addition reactions are viable for actinide elements., (© 2024 Wiley-VCH GmbH.)

A salt metathesis synthetic strategy is used to access rare tantalum/coinage metal (Cu, Ag, Au) heterobimetallic complexes. Specifically, complex [Li(THF) 2 ][Ta(C t Bu)(CH 2 t Bu) 3 ], 1 , reacts with (IPr)MCl (M = Cu, Ag, Au, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to afford the alkylidyne-bridged species [Ta(CH 2 t Bu) 3 (μ-C t Bu)M(IPr)] 2-M . Interestingly, π-bonding of group 11 metals to the Ta─C moiety promotes a rare alkylidyne alkyl to bis-alkylidene tautomerism, in which compounds 2-M are in equilibrium with [Ta(CH t Bu)(CH 2 t Bu) 2 (μ-CH t Bu)M(IPr)] 3-M . This equilibrium was studied in detail using NMR spectroscopy and computational studies. This reveals that the equilibrium position is strongly dependent on the nature of the coinage metal going down the group 11 triad, thus offering a new valuable avenue for controlling this phenomenon. Furthermore, we show that these uncommon bimetallic couples could open attractive opportunities for synergistic reactivity. We notably report an uncommon deoxygenative carbyne transfer to CO 2 resulting in rare examples of coinage metal ketenyl species, ( t BuCCO)M(IPr), 4-M (M = Cu, Ag, Au). In the case of the Ta/Li analogue 1 , the bis(alkylidene) tautomer is not detected, and the reaction with CO 2 does not cleanly yield ketenyl species, which highlights the pivotal role played by the coinage metal partner in controlling these unconventional reactions.