Polymeric Structure of Oxalato-Bridged Complexes of Tetravalent Actinides Th, U, Np and Pu

Andreev, G. B.; Budantseva, N. A.; Федосеев, А. М.; Moisy, Philippe

doi:10.1021/ic201313g

Cited by 40 publications

(48 citation statements)

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“…The distance between adjacent Th atoms within the same chains is about 6.607 Å, and the shortest distance between Th atoms that belong to different chains is about 9.576 Å. Similar 1D polymeric structures were also found in orthorhombic K 4 [U(C 2 O 4 ) 4 ] · 4H 2 O,24 triclinic K 4 [Th(C 2 O 4 ) 4 ] · 4H 2 O25 and {C(NH 2 ) 3 } 4 [An(C 2 O 4 ) 4 ] · 2H 2 O (An = Th, U, Np, Pu) 26. The coordination to the Th atoms greatly influences the length of C–O bonds in oxalato ligands.…”

Section: Resultssupporting

confidence: 69%

“…In the case of double An IV oxalates with alkali/alkaline earth ions, a monomeric structure with a CN of 9, Ba 2 [U(C 2 O 4 ) 4 (H 2 O)] · 7H 2 O,23 and polymeric chains with a CN of 10, K 4 [U(C 2 O 4 ) 4 ] · 4H 2 O24 and K 4 [Th(C 2 O 4 ) 4 ] · 4H 2 O,25 were also reported. Isostructural [C(NH 2 ) 3 ] 4 [An(C 2 O 4 ) 4 ] · 2H 2 O (An = Th, U, Np, Pu)26 have polymeric chains similar to the above K + counterpart of double Th oxalate. A Pu IV oxalate with a hydroxy group, KPu(C 2 O 4 ) 2 (OH) · 2H 2 O, was characterized 27.…”

Section: Introductionmentioning

confidence: 99%

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Spectroscopic Studies and Crystal Structures of Double Thorium(IV) Oxalates with Sodium Ions

et al. 2013

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Section: Resultssupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Spectroscopic Studies and Crystal Structures of Double Thorium(IV) Oxalates with Sodium Ions

et al. 2013

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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: 77%

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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“…Bis-Schiff bases derived from salicylaldehyde and its derivatives with diamines are a kind of versatile ligands in coordination chemistry. The preferred way to construct polynuclear complexes is the use of suitable bridging groups, such as 3 N , − NCS -, 2 N(CH) , − dicarboxylate, 4,4′-bipy, and so on [4][5][6][7]. Among the bridging groups, the azide ligand has received particular interest because it is very useful to design extended polynuclear complexes.…”

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confidence: 99%

Crystal structure of an end-on azido-bridged polymeric zinc(II) complex

2015

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A new end-on azido-bridged polymeric zinc(II) complex [Zn 2 ClL(μ 1,1 -N 3 )] n , where L is the dianionic form of N,N′-bis(5-fluoro-2-hydroxybenzylidene)-2-hydroxy-1,3-propanediamine, is prepared and structurally characterized by elemental analysis and single crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P2 1 /c, with unit cell dimensions a = 9.194(1) Å, b = 22.356(2) Å, c = 9.598(1) Å, β = 95.869(3)°, V = 1962.5(4) Å 3 , Z = 4, R 1 = 0.0691, and wR 2 = 0.1642. The inner Zn atom of the [Zn 2 ClL] unit is coordinated by the imino N and phenolate O atoms of L and one azido N atom, forming a square pyramidal geometry. The outer Zn atom of the [Zn 2 ClL] unit is coordinated by two phenolate O of L, one Cl ligand, and one N atom of the bridging azide group, forming a tetrahedral geometry. The Zn⋯Zn distance in the [Zn 2 ClL] unit is 3.072(2) Å. The [Zn 2 ClL] units are linked through end-on azido bridges, forming 1D chains running along the c axis. Polymeric structures of complexes with bridging groups are currently attracting much attention for their interesting structures and wide applications [1-3]. Bis-Schiff bases derived from salicylaldehyde and its derivatives with diamines are a kind of versatile ligands in coordination chemistry. The preferred way to construct polynuclear complexes is the use of suitable bridging groups, such as 3 N , − NCS -, 2 N(CH) , − dicarboxylate, 4,4′-bipy, and so on [4-7]. Among the bridging groups,the azide ligand has received particular interest because it is very useful to design extended polynuclear complexes. It can bind up to three metal atoms when acting as a monatomic bridge (end-on, EO) and up to six using the two terminal nitrogen atoms to bridge (end-to-end, EE) (Scheme 1) [8][9][10]. A major obstacle to a more comprehensive study of such azide-based polymeric coordination complexes is the lack of rational synthetic procedures, since with the present state of knowledge it is hardly possible to determine which coordination mode will be adopted by the azide ligand and whether the sought-after alternating chain structure will finally be formed or not. Hydrogen bonds are known as an important factor for the selfassembly of complexes [11][12][13]. N,N′-Bis(2-hydroxybenzylidene)-2-hydroxy-1,3-propanediamine and its derivatives have been used as bis-Schiff bases in the construction of complexes with various metal atoms [14][15][16][17]. However, no zinc complexes derived from such bis-Schiff bases have been reported. As a continuation of the work on the self-assembly preparation of azido-bridged polymeric complexes, in this paper, a new end-on azido-bridged polymeric zinc(II) complex [Zn 2 ClL(μ 1,1 -N 3 )] n , where L is the dianionic form of N,N′-bis(5-fluoro-2-hydroxybenzylidene)-2-hydroxy-1,3-propanediamine (H 2 L, Scheme 2), was prepared and structurally characterized.

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Polymeric Structure of Oxalato-Bridged Complexes of Tetravalent Actinides Th, U, Np and Pu

Cited by 40 publications

References 43 publications

Spectroscopic Studies and Crystal Structures of Double Thorium(IV) Oxalates with Sodium Ions

Spectroscopic Studies and Crystal Structures of Double Thorium(IV) Oxalates with Sodium Ions

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

Crystal structure of an end-on azido-bridged polymeric zinc(II) complex

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