Chalcogen Bonding of SO₂ and s‐Block Metal Iodides Near Room Temperature: A Remarkable Structural Diversity

Abstract

In this contribution we have systematically explored the coordination chemistry of the iodide anion towards SO 2. While employing large organocations like s-block metal complexes of crown-ethers, we discovered a remarkable structural diversity within the herein characterized compounds together with novel architectures of SO 2 solvates. The observed O 2 S•••Iinteractions are observed to be strong enough to determine the crystal packing and dimensionality. In the light of chalcogen bonding, the small molecule SO 2 is introduced as a supramolecular synthon. In the light of a chemistry in non-aqueous solutions, the ISO 2 anion is revisited. Chalcogen bonding was established to form one-dimensional networks in the compounds [Li([12]crown-4)H 2 O]I•SO 2 (1), [Na([15]crown-5)(SO 2)I] (2), [K([18]crown-6)(SO 2)I] (4), [NH 4 ([18]crown-6)]I•SO 2 (5), [Rb([18]crown-6)I(SO 2)]•2SO 2 (6) and [Cs([18]crown-6)(SO 2) 2 I] (7) all of which were obtained by 1:1 complexation of the respec-[a]

Coordination Chemistry and Spectroscopic Properties of Eu(II), Sm(II), and Yb(II) with 12-Crown-4

“…The Yb 2+ metal center is fully encapsulated by two tetradentate 12c4 molecules, without any coordinating solvent molecules (see Figure ). This is a rather commonly observed motif for homoleptic 12-crown-4 sandwiches with alkali, , select alkaline earth, , divalent transition metals and Ag + , , as well as p-block metals such as Ge 2+ , Sn 2+ , In 3+ , and Tl + all forming [M­(12c4) 2 ] m + ( m = 1, 2, 3) cations with various outer-sphere anions . Despite the common cation assembly, the asymmetric unit of this structure contains two [Yb­(12c4) 2 ] 2+ and four [Ph 4 B] − ions, which are all crystallographically distinct.…”

Deoxygenation of chalcogen oxides EO2 (E = S, Se) with phospha-Wittig reagents

“…4 Flue gas desulfurization requires effective interactions of a certain material with SO 2 and several strategies have been developed to sequester SO 2 at ambient conditions. From the perspective of a main-group chemist, SO 2 binding [5][6][7][8][9][10][11][12][13][14][15] and activation, [16][17][18][19][20][21] conversion and/or reduction, [22][23][24][25][26][27][28] but also sorption [29][30][31][32][33] have been realized.…”

Deoxygenation of chalcogen oxides EO2 (E = S, Se) with phosphaWittig reagents

“…From the perspective of a main-group chemist, SO2 binding [5][6][7][8][9][10][11][12][13][14][15] and activation, [16][17][18][19][20][21] conversion and/or reduction, [22][23][24][25][26][27][28] but also sorption [29][30][31][32][33] have been realized. Furthermore, the functionalization with SO2 building blocks has been achieved in various small organic molecules over time.…”