A Rare Tetranuclear Thorium(IV) μ₄‐Oxo Cluster and Dinuclear Thorium(IV) Complex Assembled by Carbon–Oxygen Bond Activation of 1,2‐Dimethoxyethane (DME)

Abstract

The synthesis and X-ray crystal structure of two new multinuclear thorium complexes are reported. The tetranuclear μ4 -oxo cluster complex Th4 (μ4 -O)(μ-Cl)2 I6 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]6 and the dinuclear complex Th2 I5 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]3 (DME) (DME=dimethoxyethane) are formed by CO bond activation of 1,2-dimethoxyethane (DME) mediated by thorium iodide complexes.

Protactinium and the intersection of actinide and transition metal chemistry

“…Within the actinide peroxide literature, this structural motif is unique, the majority of the observed actinide peroxide structures taking on significant curvature as a result of both the peroxide ligand, the actinyl oxygen, and more distant interactions with charge compensating cations in these complexes forming nanospheres, belts, and in some cases fullerene-like connectivities to name only a few 29 . The formation of discrete tetranuclear metal clusters about a tetrahedral oxygen atom are rare for the actinides with few examples known to date 31 . However, a variety of tetranuclear Ce(IV) complexes with a tetrahedral motif are known 32 , 33 .…”

Thorium coordination: A comprehensive review based on coordination number

“…The soluble actinide-halide complexes are regularly explored due to them being possible starting materials for other compounds [39] lead Kiplinger et al to begin developing methods that did not require thorium metal as a starting material. [40] This was done in prior reports [39b] through the reaction of ThCl 4 (DME) 2 , where DME = 1,2-dimethoxyethane, and trimethylsilyl iodide via complete halide exchange to give ThI 4 (DME) 2 . The halide exchange product can then react with excess DME to give the dinuclear thorium complex, Th 2 I 5 [κ 2 (O,O')-µ-O(CH 2 ) 2 OCH 3 ] 3 (DME), 18.…”

Th(IV) complexes with cis-ethylenebis(diphenylphosphine oxide): X-ray structures and NMR solution studies

“…[3] There has also been a wide variety of reports directed toward the use of Th(IV) complexes as catalysts for chemical transformations. [4] A selection of reactions mediated by Th(IV) organometallic complexes include: C-H and C-O bond activation, [5,6] hydrosilylation of alkenes and alkynes, [7] hydroamination, [7][8][9][10] aldehyde dimerization, [11] and phosphonoester hydrolysis. [12] To this end, investigations into the synthesis and structure of high-denticity Th(IV) complexes will contribute to each of the diverse set of chemical areas described above.…”