The Crystal and Molecular Structure of alpha-Tetrakis (acetylacetonato)thorium(IV).

Allard, Bert; Nygren, Martin; Valde, Gunnar; Andresen, Arne F.; Sandström, M.

doi:10.3891/acta.chem.scand.30a-0461

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“…33 Interestingly, this ligand arrangement is not the calculated energy minimum for a M(bidentate) 4 complex with square antiprismatic geometry (llll). 33 The stereochemistry of complexes 1, 2, and 4 also differs from the previously reported α-Th(acac) 4 , 34 which adopts a dodecahedral gggg arrangement, as well as β-U(acac) 4 35 and β-Np(acac) 4 , 36 both of which adopt square antiprismatic ssss stereochemistry. We believe the ssll ligand arrangement for complexes 1, 2, and 4 is required to accommodate packing of the bulky aryl groups on the Ar acnac The isostructural nature of complexes 1, 2, and 4 allows for a rare direct comparison of solid-state metrical parameters going across the actinide series from Th to U, and from U to Pu (we expect that compound 3, the Np complex, would also be isostructural, but the crystals were not of sufficient quality to allow X-ray structural determination).…”

Section: ■ Results and Discussioncontrasting

confidence: 60%

“…Interestingly, this ligand arrangement is not the calculated energy minimum for a M(bidentate) 4 complex with square antiprismatic geometry ( llll ) . The stereochemistry of complexes 1 , 2 , and 4 also differs from the previously reported α-Th(acac) 4 , which adopts a dodecahedral gggg arrangement, as well as β-U(acac) 4 and β-Np(acac) 4 , both of which adopt square antiprismatic ssss stereochemistry. We believe the ssll ligand arrangement for complexes 1 , 2 , and 4 is required to accommodate packing of the bulky aryl groups on the Ar acnac ligands, which is not a factor in the O,O donor β-diketonate acac ligand.…”

Section: Resultsmentioning

confidence: 60%

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Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An^IV(^Aracnac)₄Complexes (An = Th, U, Np, Pu;^Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-^tBu₂C₆H₃)

Schnaars

Gaunt²,

Hayton

et al. 2012

Inorg. Chem.

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A series of tetravalent An(IV) complexes with a bis-phenyl β-ketoiminate N,O donor ligand has been synthesized with the aim of identifying bonding trends and changes across the actinide series. The neutral molecules are homoleptic with the formula An((Ar)acnac)(4) (An = Th (1), U (2), Np (3), Pu (4); (Ar)acnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-(t)Bu(2)C(6)H(3)) and were synthesized through salt metathesis reactions with actinide chloride precursors. NMR and electronic absorption spectroscopy confirm the purity of all four new compounds and demonstrate stability in both solution and the solid state. The Th, U, and Pu complexes were structurally elucidated by single-crystal X-ray diffraction and shown to be isostructural in space group C2/c. Analysis of the bond lengths reveals shortening of the An-O and An-N distances arising from the actinide contraction upon moving from 1 to 2. The shortening is more pronounced upon moving from 2 to 4, and the steric constraints of the tetrakis complexes appear to prevent the enhanced U-O versus Pu-O orbital interactions previously observed in the comparison of UI(2)((Ar)acnac)(2) and PuI(2)((Ar)acnac)(2) bis-complexes. Computational analysis of models for 1, 2, and 4 (1a, 2a, and 4a, respectively) concludes that both the An-O and the An-N bonds are predominantly ionic for all three molecules, with the An-O bonds being slightly more covalent. Molecular orbital energy level diagrams indicate the largest 5f-ligand orbital mixing for 4a (Pu), but spatial overlap considerations do not lead to the conclusion that this implies significantly greater covalency in the Pu-ligand bonding. QTAIM bond critical point data suggest that both U-O/U-N and Pu-O/Pu-N are marginally more covalent than the Th analogues.

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Section: ■ Results and Discussioncontrasting

confidence: 60%

Section: Resultsmentioning

confidence: 60%

Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An^IV(^Aracnac)₄Complexes (An = Th, U, Np, Pu;^Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-^tBu₂C₆H₃)

Schnaars

Gaunt²,

Hayton

et al. 2012

Inorg. Chem.

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Enumeration by pólya's theorem of the isomerism in eight-coordinate complexes in square antiprismatic, triangular dodecahedral and hendecahedral (bicapped trigonal prismatic) geometries

Haigh

1996

Polyhedron

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Structures of high coordination complexes

Drew

1977

Coordination Chemistry Reviews

328

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The Crystal and Molecular Structure of alpha-Tetrakis (acetylacetonato)thorium(IV).

Cited by 4 publications

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Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An^IV(^Aracnac)₄Complexes (An = Th, U, Np, Pu;^Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-^tBu₂C₆H₃)

Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An^IV(^Aracnac)₄Complexes (An = Th, U, Np, Pu;^Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-^tBu₂C₆H₃)

Enumeration by pólya's theorem of the isomerism in eight-coordinate complexes in square antiprismatic, triangular dodecahedral and hendecahedral (bicapped trigonal prismatic) geometries

Structures of high coordination complexes

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The Crystal and Molecular Structure of alpha-Tetrakis (acetylacetonato)thorium(IV).

Cited by 4 publications

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Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of AnIV(Aracnac)4Complexes (An = Th, U, Np, Pu;Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-tBu2C6H3)

Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of AnIV(Aracnac)4Complexes (An = Th, U, Np, Pu;Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-tBu2C6H3)

Enumeration by pólya's theorem of the isomerism in eight-coordinate complexes in square antiprismatic, triangular dodecahedral and hendecahedral (bicapped trigonal prismatic) geometries

Structures of high coordination complexes

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Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An^IV(^Aracnac)₄Complexes (An = Th, U, Np, Pu;^Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-^tBu₂C₆H₃)

Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An^IV(^Aracnac)₄Complexes (An = Th, U, Np, Pu;^Aracnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-^tBu₂C₆H₃)