Synthesis and Structure of a Terminal Uranium Nitride Complex

King, David M.; Tuna, Floriana; McInnes, Eric J. L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

doi:10.1126/science.1223488

Cited by 325 publications

(295 citation statements)

References 36 publications

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“…A recent development in this field is the synthesis of a terminal cerium (IV) oxide supported by the sterically encumbering Kläui tripodal ligand [CoCp(P(O)(OEt)2)3] and stabilized by hydrogen bonding with a molecule of acetamide (So et al, 2014). These developments, as well as the report of transient (Thomson et al, 2010) and isolated (King et al, 2012) uranium nitride complexes, bide well for the discovery of other interesting bonding motifs with f elements. Recently, a P 3--containing rare earth complex, [K(toluene)](-I)4[Y4(THF)4(-PAr)4YI](-P) (Ar = 2,6-di-iso-Pr-C6H3), was isolated from YI2(THF)3 (P[SiMe3][Ar]) (Chart 3) (Lv et al, 2011).…”

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Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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“…[14] We also noted that, as PH is sterically unencumbered, a sterically demanding metal-ligand fragment would be required to compensate for the lack of kinetic protection at phosphorus. Given our success in stabilizing terminal uranium-nitrides, [15] [16] as the THF and BPh 4 À groups are labile. [17] Treatment of 1 with NaPH 2 afforded, after work-up and recrystallization from iso-hexane, yellow crystals of the uranium(IV) parent terminal phosphide complex [U(Tren TIPS )(PH 2 )] (2) in 89% yield (Scheme 1).…”

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Triamidoamine–Uranium(IV)‐Stabilized Terminal Parent Phosphide and Phosphinidene Complexes

et al. 2014

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Terminal metal phosphinidene complexes (L n M = PR) are, despite continued interest, far less developed than their isolobal metal imide and alkylidene counterparts.[1] Although the first L n M=PR complex was reported over a quarter of a century ago, [2] sterically demanding R-groups are required, as M=PR linkages are reactive and require kinetic stabilization.[3] Certainly, free phosphinidenes (PR) are usually very reactive owing to their triplet ground states and unsaturated valence shells.[4] Although stabilization of a triplet PR group by a triplet metal fragment to generate a formal M=P bond is an attractive strategy, unlike the well-known L n M=NH and L n M=CH 2 linkages, [5] there has never been a structurally authenticated report of a d-/f-block metal-stabilized terminal parent phosphinidene L n M = PH, [6,7] and studies of such species are limited to computational investigations. [8] This paucity is underscored by a triplet-singlet energy gap of 22 kcal mol À1 for free PH, [4b] which has only been observed transiently in the gas phase or low temperature matrices. [4a, 9]

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“…In addition, convenient synthetic methods, usually involving salt elimination, are also readily available for the straightforward installation of p-ligands, such as cyclopentadienyl and cyclo-octatetraenide, into the coordination sphere of lanthanides. For uranium, there has been intense interest in uranium p-ligand interactions because of the possibility of greater covalent metal-ligand bonding compared with the lanthanides and the implications for f-orbital bonding theory and reactivity [12][13][14][15][16][17] . Nonetheless, with the notable exception of cyclopentadienyl derivatives, progress has generally been hampered by a lack of synthetic methods or suitable ligand transfer reagents.…”

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Reductive assembly of cyclobutadienyl and diphosphacyclobutadienyl rings at uranium

et al. 2013

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Despite the abundance of f-block-cyclopentadienyl, arene, cycloheptatrienyl and cyclooctatetraenide complexes, cyclobutadienyl derivatives are unknown in spite of their prevalence in the d-block. Here we report that reductive [2 þ 2]-cycloaddition reactions of diphenylacetylene and (2,2-dimethylpropylidyne)phosphine with uranium(V)-inverted sandwich 10p-toluene tetra-anion complexes results in the isolation of inverted sandwich cyclobutadienyl and diphosphacyclobutadienyl dianion uranium(IV) complexes. Computational analysis suggests that the bonding is predominantly electrostatic. Although the c 4 molecular orbital in the cyclobutadienyl and diphosphacyclobutadienyl ligands exhibits the correct symmetry for d-bonding to uranium, the dominant covalent contributions arise from p-bonding involving c 2 and c 3 orbital combinations. This contrasts with uranium complexes of larger arenes and cyclo-octatetraenide, where d-bonding dominates. This suggests that the angular requirements for uranium to bond to a small four-membered ring favours p-bonding, utilizing 5f-instead of 6d-orbitals, over d-bonding that is favoured with larger ligands, where 6d-orbitals can become involved in the bonding.

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Synthesis and Structure of a Terminal Uranium Nitride Complex

Cited by 325 publications

References 36 publications

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Triamidoamine–Uranium(IV)‐Stabilized Terminal Parent Phosphide and Phosphinidene Complexes

Reductive assembly of cyclobutadienyl and diphosphacyclobutadienyl rings at uranium

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