Hafnium(IV) complexation with oxalate at variable temperatures

Friend, Mitchell T.; Wall, Nathalie A.

doi:10.1515/ract-2016-2686

Cited by 2 publications

(2 citation statements)

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“…Hf oxalate solutions and solids have been less studied; rather, they are generally considered to be isostructural with Zr. One mononuclear Hf tetrakis complex has been reported, , in addition to solution studies . In all of these reported compounds, the metals are eight-coordinate with four side-on-bonded oxalate ligands.…”

Section: Introductionmentioning

confidence: 93%

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Countercation-Controlled Nuclearity of Zr/Hf Peroxo Oxalates

Kozma

Zakharov

Nyman

2020

Crystal Growth & Design

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Understanding fundamental differences between zirconium and hafnium chemistry contributes to our fundamental understanding of the periodic table and leads to devising necessary separations for high-precision nuclear and microelectronics applications, developing water-based nanolithographic processes, and creating new robust metal−organic frameworks for catalysis and separations. Here we crystallize a rich matrix of polynuclear Zr and Hf species differentiating in complexation with peroxide and oxalate in mild acid, where the countercations influence polymerization. Hf only complexes oxalate, yielding polymericNa 6 [Hf 2 (OH) 2 (C 2 O 4 ) 6 ], and Li 2 K 4 [Hf 2 (OH) 2 (C 2 O 4 ) 6 ] and mononuclear K 4 Hf(C 2 O 4 ) 4 , Rb 4 Hf(C 2 O 4 ) 4 , and Cs 4 Hf-(C 2 O 4 ) 4 . Zr complexes both peroxide and oxalate to yield the ring structures (N-( C H 3 ) 4 ) 6 [ Z r 6 ( O 2 ) 6 ( O H ) 6 ( C 2 O 4 ) 6 ] , L i 1 2 [ Z r 8 ( O 2 ) 1 2 ( O H ) 4 ( C 2 O 4 ) 8 ] , K 18 [Zr 12 (O 2 ) 18 (OH) 6 (C 2 O 4 ) 12 ], and Rb 24 [Zr 16 (O 2 ) 24 (OH) 8 (C 2 O 4 ) 16]. The Zr ring nuclearity increases with countercation size, while Hf polymerization decreases with increasing countercation size. The Zr rings feature nine-coordinate face-sharing polyhedra in both solution and the solid state, unprecedented in Zr coordination complexes. These studies describe differentiating the coordination chemistry of Zr/Hf, exploiting simple aqueous reagents that could be further developed for aqueous synthesis of materials as well as challenging chemical separations.

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Section: Introductionmentioning

confidence: 93%

“…One mononuclear Hf tetrakis complex has been reported, 39,43 in addition to solution studies. 44 In all of these reported compounds, the metals are eight-coordinate with four side-on-bonded oxalate ligands.…”

Section: ■ Introductionmentioning

confidence: 98%