Reactivity of a Lewis Base Supported Thorium Terminal Imido Metallocene toward Small Organic Molecules

Zhang, Congcong; Yang, Pikun; Zhou, Enwei; Deng, Xiaojie; Zi, Guofu; Walter, Marc D.

doi:10.1021/acs.organomet.7b00212

Cited by 42 publications

(31 citation statements)

References 130 publications

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“…This suggests that there is more Mo-CO backbonding present in 1-6 than UClMo/UIMo/ThClMo/ThIMo suggesting that the effective replacement of a phosphine and metal-metal linkage with the formally datively bound ketimido center leads to more electron-rich molybdenum centers in 1-6. The C=N stretches of the ketimido linkage in 1-6 are observed between 1594-1632 cm -1 , which, where data are available, is consistent with other reported actinide ketimido linkages (range 1579-1631 cm -1 ), 50,51,56,[59][60][61][62][63][65][66][67][68][69] but they are are otherwise unremarkable.…”

Section: Spectroscopic Characterizationsupporting

confidence: 89%

“…Whilst it can be reasoned that a P- type ligand bridging between an actinide and a transition metal. 72 The activation of acetonitrile and other nitriles to afford ketimides by An-X bonds is not unprecedented, [50][51][52][53][54][55]58,61,79 reacts by displacing NCMe to give the tris-paddlewheel structures which then react intermolecularly with NCMe to afford 1-4. However in the case of the iodide derivatives, it is possible that before the NCMe is dissociated from the molybdenum center and the third paddlewheel linkage is formed, the acetonitrile undergoes nucleophilic attacked by the amide of a bridging phosphino-amide rather than the phosphine lone pair, as in 1-4.…”

Section: Discussionmentioning

confidence: 99%

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Preparation of Heterobimetallic Ketimido-Actinide-Molybdenum Complexes

et al. 2019

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During our attempts to prepare paddlewheel actinide-molybdenum complexes of the type [(X)An(MesNPR 2 ) 3 Mo(CO) 3 ] (Mes= 2,4,6-trimethylphenyl; X= Cl or I; An = U or Th; R = i Pr or Ph) we have found that under certain conditions acetonitrile insertion reactions occur to give the hetero-bimetallic bridging ketimido species [ClAn(µ-MesNP i Pr 2 ) 2 (µ-MesNP i Pr 2 {µ-NCMe})Mo(CO) 3 ] (An = U, 1; Th, 2), [ClAn(µ-MesNPPh 2 ) 2 (µ-MesNPPh 2 {µ-NCMe})Mo(CO) 3 ] (An = U, 3; An = Th, 4), and [IAn(η 2 -MesNP i Pr 2 )(µ-MesNP i Pr 2 ){µ-NC(Me)N(Mes)P i Pr 2 }Mo(CO) 3 ] (An = U, 5; Th, 6). Structural and spectroscopic data confirms the assignment of a ketimido ligand bridging An(IV) and Mo(0) centers. The isolation of 1-6 is in contrast to our previously reported preparations of [(X)An(MesNPPh 2 ) 3 Mo(CO) 3 ] (

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Section: Spectroscopic Characterizationsupporting

confidence: 89%

Section: Discussionmentioning

confidence: 99%

Preparation of Heterobimetallic Ketimido-Actinide-Molybdenum Complexes

et al. 2019

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“…A similar trend was observed for uranium analogues 80 . According to Pyykkö, the sum of the single and double bond covalent radii of thorium and nitrogen are 2.46 and 2.03 Å 82 , respectively; despite their bridging natures, the Th = N distances above are closer to the double than single bond values suggesting multiple bond interactions, and they compare favourably to terminal Th–N imido distances that span the range 2.034–2.165 Å 19,20,22,23,26,28–30 . The strong donor nature of the imido units in 4M is also suggested by the Th–N amine bond lengths, which are now ~2.745 Å, some 0.07 Å longer than the analogous distance in 2 .…”

Section: Resultsmentioning

confidence: 91%

Thorium-nitrogen multiple bonds provide evidence for pushing-from-below for early actinides

Alvarez-Lamsfus

Wildman

et al. 2019

Nat Commun

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Although the chemistry of uranium-ligand multiple bonding is burgeoning, analogous complexes involving other actinides such as thorium remain rare and there are not yet any terminal thorium nitrides outside of cryogenic matrix isolation conditions. Here, we report evidence that reduction of a thorium-azide produces a transient Th≡N triple bond, but this activates C-H bonds to produce isolable parent imido derivatives or it can be trapped in an N-heterocycle amine. Computational studies on these thorium-nitrogen multiple bonds consistently evidences a σ > π energy ordering. This suggests pushing-from-below for thorium, where 6p-orbitals principally interact with filled f-orbitals raising the σ-bond energy. Previously this was dismissed for thorium, being the preserve of uranium-nitrides or the uranyl dication. Recognising that pushing-from-below perhaps occurs with thorium as well as uranium, and with imido ligands as well as nitrides, suggests this phenomenon may be more widespread than previously thought.

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“…] is the rst nitrido complex reported for thorium. However, several thorium imido complexes have been structurally characterized [30][31][32][33][34][35][36]. Generally, these complexes feature shorter Th-N bonds than those of [Na][1].Fig.…”

mentioning

confidence: 99%