Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses

Ziegelgruber, Kate L.; Knope, Karah E.; Frisch, Mark; Cahill, Christopher L.

doi:10.1016/j.jssc.2007.12.008

Cited by 76 publications

(52 citation statements)

References 116 publications

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“…7 As a result of this superimposition, metrical parameters describing the carbonate unit cannot be reliably reported, however, the rest of the structure can be accurately described. Th( [32][33][34][35][36] The Th-O oxalate bond distances in 4 lie just outside the lower range of those found in the latter (2.481(2)-2.578(7) Å), whilst the O-C oxalate bond distances in 4 are above the upper range of those found in the inorganic oxalates (1.242(3)-1.261(4) Å). The Th1-O1 and Th1-O2 bond distances are virtually identical (2.473(2) and 2.475(3) Å respectively), as are the O1-C001 and O2-C001 bond distances (1.264(4) and 1.260(4) Å respectively).…”

Section: Andmentioning

confidence: 79%

Mixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity

et al. 2015

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The Th(iv) mixed-sandwich halide complexes Th(COT(TIPS2))Cp*X (where COT(TIPS2) = 1,4-{Si(i)Pr(3)}(2)C(8)H(6), X = Cl, I) have been synthesised, and structurally characterised. When Th(COT(TIPS2))Cp*I is reduced in situ in the presence of CO(2), a mixture of dimeric carboxylate and oxalate complexes {Th(COT(TIPS2))Cp*}(2)(μ-κ(1):κ(2)-CO(3)) and {Th(COT(TIPS2))Cp*}(2)(μ-κ(2):κ(2)-C(2)O(4)) are formed, possibly via a transient Th(iii) species. Th(COT(TIPS2))Cp*Cl is readily alkylated to yield the benzyl complex Th(COT(TIPS2))Cp*CH(2)Ph, which reacts with CO(2) to form a carboxylate and with H(2) to form a hydride; the latter inserts CO(2), giving the bridging formate complex {Th(COT(TIPS2))Cp*(μ-κ(1):κ(1)-O(2)CH)}(2).

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Section: Andmentioning

confidence: 79%

Mixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity

et al. 2015

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“…The rational design and construction of coordination polymers with unique structural motifs and unique chemical and physical properties have attracted extensive interest in supramolecular and materials chemistry [1][2][3]. In the past decade, plenty of metalorganic hybrids exhibiting fascinating structures have been synthesized [4][5][6].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of triaqua-(pyrazine-2,3-dicarboxylato)cerium(III), Ce(H2O)3(C6H2N2O4)

Feng¹,

Zhao²,

Shi³

et al. 2010

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe mixture of Ce(NO 3)3 (0.038 g, 0.1 mmol) and 2,3-pyrazinedicarboxylic acid (0.034 g, 0.2 mmol), was stirred into 15 ml water. Then the pH was adjusted to approx. 5with 1.Msolution of NaOH, and 3mlethanol solution of 4,4'-bipyridine (4,4'-bipy, 0.2 mmol) was added. The reaction mixture was heated on awater bath for 10 hat70°C, then filtered. The resulting clear solution was diffused with diethyl ether vapor at room temperature for two weeks. Yellow crystals were obtained (yield, 0.013 g, 36 . %). The products are insoluble in water and common solvents. Elemental analysis -found: C, 20.62.%; H, 2.28.%; N, 7.84 %; calculated for C 6H8CeN2O7:C ,20.01 %; H, 2.24 %; N, 7.76 %. IR data are available in the CIF. DiscussionThe rational design and construction of coordination polymers with unique structural motifs and unique chemical and physical properties have attracted extensive interest in supramolecular and materials chemistry [1][2][3]. In the past decade, plenty of metalorganic hybrids exhibiting fascinating structures have been synthesized [4][5][6]. Some studies on di-and multi-carboxyl ligands or multifunctional carboxyl-containing ligands incorporating other coordination groups, such as N, Sh ave been reported [7,8]. Pyrazine is well-known as abridging ligand, especially in lowdimensional materials. When coordinated to metallic ions, it affords awide variety of polynuclear compounds. Carboxylic acid ligands are also capable of bridging and providing effective magnetic exchange pathway. When the two ligands are combined, such as pyrazinecarboxylic acid, pyrazine dicarboxylic acid and pyrazine teracarboxylic acid, it is very likely to obtain some structurally novel and magnetically interesting complexes. For the lanthanide complexes based on 2,3-pyrazonedicarboxylic acid, just several examples were previously reported [9]. Because the lanthanide ions generally have higher coordination numbers than the d-block metal ions, it is more likely to incorporate ancillary ligands into lanthanide coordination networks. Such ancillary ligands may be removed keeping the lanthanide-organic framework intact, thereby generating porous solids with coordinatively unsaturated lanthanide ions that may have potential catalytic activity. The asymmetric unit of the title complex consists of one Ce(III) cation, one 2,3-pyrazinedicarboxylate ligand, and three coordi- , and their coordination modes are essentially different. Maybe, this is due to the effect of lanthanide contraction [11]. 2,3-Pyrazinedicarboxylate ligand acts as tetra-dentate bridge pillar mode to connect two adjacent Ce1 and Ce1A ions in abridge mode, and thus affords athree connecting node, the carboxylate groups coordinate to the metal atoms in either bridging or chelating fashion. 2,3-Pyrazinedicarboxylate ligand chelate the central ion forming five-and afour-membered ring around the Ce(III). These rings are nearly perpendicular to each other. The bond angles of O2− Ce1−O4, O2−Ce1−N1, O4−Ce1−N1 are 175.9(2)°,1 04.0(2)°a nd 72.0(2)°,r espectively...

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Section: Discussionmentioning

confidence: 99%

Crystal structure of diaqua-bis(hydrogen 2-propyl-1H-imidazole-4,5-dicarboxylato)calcium(II), Ca(H2O)2(C8H9N2O4)2

Feng¹,

Miao²,

Li³

et al. 2010

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe mixture of Ca(NO 3 ) 2. · . 4H 2 O( 0.024 g, 0.1 mmol) and 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H 2L, 0.041 g, 0.2 .mmol) was stirred into 15 ml of water. Then 3mlaqueous solution of potassium hydroxide (0.0056 g, 0.1 mmol) was added to deprotonate the dicarboxylic acid. The pH was adjusted to approx. 4with 1Msolution of nitric acid. After stirring for 20 min in air and then the mixture was placed into 25 mL Teflon-lined autoclave and heated under autogenous pressure at 160°Cf or 72 . h. The autoclave was cooled over ap eriod of 12 ha tar ate 5 .°C/h. After the mixture was slowly cooled to room temperature, colourless crystals were obtained, the products are stable in air and insoluble in water (yield 0.017 g, 36 %based on the calcium element). Elemental analysis -found: C, 40.82 %; H, 4.78 %; N, 11.85 %; calculated for C 16H22N4O10Ca: C, 40.84 %; H, 4.71 %; N, 11.90 %. IR data are available in the CIF. DiscussionThe rational design and construction of coordination polymers with unique structural motifs and unique chemical and physical properties have attracted extensive interest in supramolecular and materials chemistry [1][2][3]. In the past decade, plenty of metalorganic hybrids exhibiting fascinating structures have been synthesized [4][5][6][7]. Some studies on di-and multi-carboxyl ligands or multifunctional carboxyl-containing ligands incorporating other coordination groups, such as N, Sh ave been reported [9,10]. Recent years, imidazole di-or multi-carboxylate have been intensively employed to provide avariety of topological architectures [9,10]. The title complex consists of one calcium(II) cation, two HL -ligands, and two coordinated water molecules. Ca(II) is octacoordinated [CaN 2 O 6 ], and has in aslightly distorted quadratic anti-prismatic coordination polyhedron formed by four oxygen atoms from the deprotonated carboxylate group of HL -ligand, two nitrogen atoms from the imidazole rings, and two oxygen atoms of water molecules. The N1 and O4 atoms chelate the Ca(II) with afive membered ring of N1/C2/C5/O4/Ca1, while O1 of the other carboxylate groups from HL -exhibits amonodentate mode to link the Ca(II) ion. The O2 and O3 atoms do not participate in the coordination. The Ca-Od istances range from 2.412(2) to 2.608(2) Å.The bond length of Ca1-Ni s2 .605(2) Å.The angles around the central Ca ∠O1i -Ca1-O1, ∠O1 i -Ca1-O5, and ∠O1-Ca1-O5 are 72.72(9)°,125.71(6)°and 71.73(6)°,respectively. The angles of ∠O5-Ca1-ii are 160.69 (8) -z+½;ii: -x+½,y-½,-z+½;iii: x+½,y-½,z;iv: x-½,y+½,z).

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Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses

Cited by 76 publications

References 116 publications

Mixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity

Mixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity

Crystal structure of triaqua-(pyrazine-2,3-dicarboxylato)cerium(III), Ce(H2O)3(C6H2N2O4)

Crystal structure of diaqua-bis(hydrogen 2-propyl-1H-imidazole-4,5-dicarboxylato)calcium(II), Ca(H2O)2(C8H9N2O4)2

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