Charge control of the inverse trans-influence

Pierre, Henry S. La; Rosenzweig, Michael W.; Kosog, Boris; Hauser, Christina; Heinemann, Frank W.; Liddle, Stephen T.; Meyer, Karsten

doi:10.1039/c5cc07211e

Cited by 29 publications

(34 citation statements)

References 52 publications

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“…For many years the ITI was limited to uranyl(VI) complexes 20 or structurally analogous complexes such as [UOCl 5 ] − (ref. 29 ), but in recent years a limited number of uranium(V) and (VI) ITI complexes have emerged 24 25 30 31 32 33 . The unifying theme has been high oxidation state (V or VI) metal complexes combined with hard, polarizing, charge-loaded oxo, imide and nitride ligands.…”

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The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

et al. 2017

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Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

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The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

et al. 2017

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“…10 This effect, termed the inverse-trans-inuence (ITI) as a general concept has become the focus of several experimental and theoretical investigations and has evolved to be primarily applied to ligands trans to multiply bonded ligands. [11][12][13][14][15][16][17] This has also been studied in the [AnOX 5 ] nÀ complexes (An ¼ Pa V , U VI , X ¼ F, Cl, Br), 18,19 where reaction of HBr with [UOCl 5 ] 1À yields [UO(Cl)Br 4 ] 1À where all of the equatorial Cl's have been replaced by Br's, but the trans-Cl is retained, which also possess the shortest M-Cl bond in the molecule. 19 These seminal studies helped to show that something was unusual with high valent actinides where a ligand was trans to an oxo ligand, though these studies have not been revisited with modern instrumentation and methods.…”

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confidence: 99%

Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

et al. 2020

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“…We also considered that the X ligand in the trans position to a ligated metal ion would provide the possibility to exploit the inverse trans influence (ITI) in the formation of stronger bonds to an atom (here the second metal) in the position trans to X, the phenomenon whereby mutually trans-ligands bind closer and more tightly to a uranium center than they would in a d-block system, since the available (pseudocore) U 6p orbitals can mix with the valence 5f. 28 − 31 …”

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confidence: 99%

Metal–Metal Bonding in Uranium–Group 10 Complexes

et al. 2016

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Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IUIV(OArP-κ2O,P)3 (2) {[ArPO]− = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IUIV(μ-OArP-1κ1O,2κ1P)3M0, M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XUIV(μ-OArP-1κ1O,2κ1P)3Ni0, X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal longer and weaker unsupported U–TM bonds vs 3.

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Charge control of the inverse trans-influence

Cited by 29 publications

References 52 publications

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

Metal–Metal Bonding in Uranium–Group 10 Complexes

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