Nitrile‐Supported Coordination Polymers of Cerium(III) Bromide

Vasudevan, Kalyan V.; Boncher, William L.; Smith, N.; Blair, Michael W.; Scott, Brian L.; Bennett, B. L.; Hehlen, Markus P.; Muenchausen, R. E.; Gordon, John C.

doi:10.1002/ejic.201400030

Cited by 8 publications

(5 citation statements)

References 27 publications

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“…Importantly, the structural characterization of 6 ·MeCN provides the first example of an unambiguous homoleptic cerium MeCN complex. Like complex 5 ·MeCN, the Ce center is also in a tricapped trigonal-prismatic geometry and the average Ce–N bond distance [2.61(1) Å] is consistent with those of 2 ·2MeCN and other cerium MeCN solvates. , Last, while complex 7 ·MeCN is the third reported homoleptic MeCN solvate of neodymium, , it is the first to provide complete X-ray crystallographic data for structural analysis, where the average Nd–N bond distance [2.57(1) Å] is consistent with other Nd–N MeCN interactions. , …”

Section: Resultsmentioning

confidence: 65%

“…Like complex 5•MeCN, the Ce center is also in a tricapped trigonal-prismatic geometry and the average Ce−N bond distance [2.61(1) Å] is consistent with those of 2• 2MeCN and other cerium MeCN solvates. 5,47 Last, while complex 7•MeCN is the third reported homoleptic MeCN solvate of neodymium, 4,39 it is the first to provide complete Xray crystallographic data for structural analysis, where the average Nd−N bond distance [2.57(1) Å] is consistent with other Nd−N MeCN interactions. 48,49 Complexes 5−7 were further characterized by CHN EA and IR spectroscopy.…”

Section: ■ Introductionmentioning

confidence: 91%

“…The average Ce−N bond distance [2.64(2) Å] in 2• 2MeCN is statistically identical with the Ce−N bond distances in both CeBr 3 (MeCN) 5 and Ce 4 Br 12 (MeCN) 11 . 5,47 Last, the average Ce−I bond distance [3.16(4) Å] is also typical of known Ce−I interactions. 20 Importantly, the solid-state molecular structure of 2 was confirmed by a separate batch of crystals isolated from dissolution of CeI 3 in MeCN at ambient temperature.…”

Section: ■ Introductionmentioning

confidence: 99%

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Early-Lanthanide(III) Acetonitrile–Solvento Adducts with Iodide and Noncoordinating Anions

Brown

Davis²,

Scott³

et al. 2015

Inorg. Chem.

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Dissolution of LnI3 (Ln = La, Ce) in acetonitrile (MeCN) results in the highly soluble solvates LnI3(MeCN)5 [Ln = La (1), Ce (2)] in good yield. The ionic complex [La(MeCN)9][LaI6] (4), containing a rare homoleptic La(3+) cation and anion, was also isolated as a minor product. Extending this chemistry to NdI3 results in the consistent formation of the complex ionic structure [Nd(MeCN)9]2[NdI5(MeCN)][NdI6][I] (3), which contains an unprecedented pentaiodide lanthanoid anion. Also described is the synthesis, isolation, and structural characterization of several homoleptic early-lanthanide MeCN solvates with noncoordinating anions, namely, [Ln(MeCN)9][AlCl4]3 [Ln = La (5), Ce (6), Nd (7)]. Notably, complex 6 is the first homoleptic cerium MeCN solvate reported to date. All reported complexes were structurally characterized by X-ray crystallography, as well as by IR spectroscopy and CHN elemental analysis. Complexes 1-3 were also characterized by thermogravimetric analysis coupled with mass spectrometry to further elucidate their bulk composition in the solid-state.

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Section: Resultsmentioning

confidence: 65%

Section: ■ Introductionmentioning

confidence: 91%

Section: ■ Introductionmentioning

confidence: 99%

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Early-Lanthanide(III) Acetonitrile–Solvento Adducts with Iodide and Noncoordinating Anions

Brown

Davis²,

Scott³

et al. 2015

Inorg. Chem.

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“…Multiple studies showed that the molecular structures of lanthanide halide complexes highly depend on the donor solvent used in the synthesis. , Coordination of small donor molecules mainly leads to mononuclear complexes. Most often, tetrahydrofuran (thf) or dimethoxyethane (dme) are used in the synthesis and fill up the coordination sphere; , pyridine or acetonitrile , are also frequently used. Hereinafter, we use “solvate” to denote a complex with coordinated solvent molecules.…”

Section: Introductionmentioning

confidence: 99%

Structural Diversity and Multielectron Reduction Reactivity of Samarium(II) Iodido-β-diketiminate Complexes Dependent on Tetrahydrofuran Content

et al. 2022

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The molecular structures of complexes [Sm(Nacnac)I-(thf) n ] (Nacnac = HC(C(Me)Ndipp) 2 − , dipp = 2,6-diisopropylphenyl, thf = tetrahydrofuran) depending on the number of thf ligands are studied. The complete removal of thf from a known complex [Sm(Nacnac)I(thf) 2 ] leads to a tetranuclear product [Sm(Nacnac)I] 4 (4). The partial removal of thf results in mixtures of dinuclear [Sm 2 (Nacnac) 2 I 2 (thf)] (2), trinuclear [Sm 3 (Nacnac) 3 I 3 (thf)] (3), and tetranuclear [Sm 4 (Nacnac) 4 I 4 (thf) 2 ] (4*) complexes and 4, depending on the conditions. The reaction of solvent-free SmI 2 with 1 equiv of K(Nacnac) results mainly in [Sm(Nacnac) 2 ] (1), while the interaction of 4 with certain amounts of thf allows obtaining pure 2 and 3 (with the admixture of 4*). Complex 4* is the exact dimer of 2, and both compounds are stable in solutions. Reactions with 3 and 4 as reductants are studied. 4 is oxidized by I 2 to stoichiometrically yield two products, mixed-valent tetranuclear [Sm 4 (Nacnac) 4 I 5 ] (5) and binuclear [Sm(Nacnac)I 2 ] 2 (6) complexes. In the reaction of 4 with n Bu 3 PTe, a trinuclear complex [Sm 3 (Nacnac) 3 (μ-I) 3 (μ 3 -E) 2 ] (8, E = I or Te) is formed in small amounts, with the formation of 6 as the second product. 3 serves as a two-electron reductant in the reaction with n Bu 3 PTe to yield a trinuclear complex [Sm 3 (Nacnac) 3 I 3 (μ-Te 2 )] (7). Complexes 2, 4, 4*, 5, 6, and 8 possess a unique flat Sm x I y core of heavy atoms, which is assumed to be a consequence of the Nacnac ligand geometry.

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“…Our group has recently developed coordination polymers of cerium(III) bromide with ligands coordinated through a nitrile group [26]. Functionalizing the pore surfaces within the mesoporous silica with a nitrile group should allow cerium bromide to bind to the matrix by forming nitrile coordination compounds at the pore surface.…”

Section: Introductionmentioning

confidence: 99%