Catching Gaseous SO₂ in Cone‐Type Lanthanide Complexes: An Unexpected Coordination Mode for SO₂ in f‐Element Chemistry

Abstract

Easy come, easy go: the first molecular SO(2) complexes of the lanthanides (Ln=Sm, Eu) have been prepared. The compounds can reversibly coordinate gaseous SO(2). Concomitant with the addition and removal of SO(2), the color of the complexes changes reversibly. The structures of the SO(2) compounds could be confirmed in solution and in the solid state.

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis, Structure, and Ligand‐Dependent Redox Behavior

“…[25] The SÀCb onds of the thiocarbonate moiety,S 1 ÀC2 and S2ÀC2, measure1 .735(10) and 1.725(10) , respectively.T he S3 atom is disordered between two positions. The main position (55% occupancy) leads to aC ÀSd istance of 1.748 (15),t he minor position (45 %o ccupancy) leads to as horter CÀSd istance of 1.630 (16).T he CÀSd istances remain in the range of previously reported trithiocarbonate complexes. [26,27] There are two previous reports of trithiocarbonatec omplexes containing fe lements, [28,29] but the complex [Eu-(BPA)(CS 3 )(dmso) 2 ]i st he first example of at rithiocarbonate complex containing a4fe lement.…”

“…[12,13] Ln 3 + complexes of tripodala minophenolates [12] and of the TPAl igand [13c, d, 14] have been reported and weres hown to promote original stoichiometric andc atalytic transformations. [15][16][17] In contrast, the complexation of divalent lanthanides by the tris(2-pyridylmethyl)amine (TPA) ligand has never been explored. Moreover, only af ew examples of Ln 2 + complexes of tripodala minobisphenolates have been reported.…”

Activation of SO2 and CO2 by Trivalent Uranium Leading to Sulfite/Dithionite and Carbonate/Oxalate Complexes

“…Employing the tacn‐anchored tris(aryloxide) chelate [(( nP,Me ArO) 3 tacn)U III ], we and others8 previously reported the stoichiometric and catalytic disproportionation of CO 2 to CO 3 2− and CO 3b. In contrast, the reductive CO 2 coupling to give oxalate complexes is considerably more uncommon and, to date, has not been realized with our tris(aryloxide) ligand systems.…”

“…Besides the commonly observed reversible metal coordination of an innocent SO 2 ligand, most SO 2 reactions explored in detail are limited to insertion chemistry into MC, MO, and MH bonds 2. Recently, the first SO 2 complex of an f ‐ element, namely, [{(( t Bu, t Bu ArO) 3 tacn)Sm III } 2 (μ‐SO 2 )] (tacn=triazacyclononane), was formed from gaseous SO 2 that was merely bound reversibly 3…”

Dithionite and sulfinate complexes from the reaction of SO2with decamethylsamarocene

“…26 In this context, the first sulfite [{(( nP,Me ArO) 3 tacn)U IV } 2 (m-k 1 :k 2 -SO 3 )] (tacn = triazacyclononane) and dithionite [{(( nP,Me ArO) 3 tacn)U IV } 2 (m-k 2 :k 2 -S 2 O 4 )] complexes of uranium from reactions with gaseous SO 2 were reported by us. 26 In this context, the first sulfite [{(( nP,Me ArO) 3 tacn)U IV } 2 (m-k 1 :k 2 -SO 3 )] (tacn = triazacyclononane) and dithionite [{(( nP,Me ArO) 3 tacn)U IV } 2 (m-k 2 :k 2 -S 2 O 4 )] complexes of uranium from reactions with gaseous SO 2 were reported by us.…”