Na⁺[Me₃NB₁₂Cl₁₁]⁻·SO₂: a rare example of a sodium–SO₂ complex

Abstract

In the title compound, Na+[Me3NB12Cl11]−·SO2 [systematic name: sodium 1-(trimethylammonio)undecachloro-closo-dodecaborate sulfur dioxide], the SO2 molecule is η 1-O-coordinated to the Na+ cation. Surprisingly, the SO2 molecule is more weakly bound to sodium than is found in other sodium–SO2 complexes and the SO2 molecule is essentially undistorted compared to the structure of free SO2. The Na+ cation has a coordination number of eight in a distorted twofold-capped trigonal prism and makes contacts to three individual boron cluster anions, resulting in an overall three-dimensional network. Although the number of known η 1-O-coordinated SO2 complexes is growing, sodium-SO2 complexes are still rare.

Reactions of Molybdenum and Tungsten Oxide Tetrafluoride with Sulfur(IV) Lewis Bases: Structure and Bonding in [WOF4]4, MOF4(OSO), and [SF3][M2O2F9] (M = Mo, W)

“…The versatile O-donor/S-acceptor behavior of SO 2 is perhaps best demonstrated by its reaction with frustrated Lewis pairs to afford zwitterionic sulfinate esters . Sulfur dioxide also behaves as an ambidentate (κ 1 -S, κ 1 -O, and η 2 -S,O) or bridging O,O ligand toward various s -, d -, and f -block metal cations, − whereas SF 4 oxidatively adds across Rh I , Ir I , and Pt 0 complexes to afford the S II F 3 ligand …”

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

“…The respective chlorides MCl · 3SO 2 (M = Rb + , Cs + ) were described lately . Yet, most of the hitherto characterized compounds were crystal structures of s‐block SO 2 adducts with different WCAs: [Li 2 {AlF(OR F ) 3 }{(Al(OR F ) 4 }] · 2SO 2 (R F = C(CF 3 ) 3 ), [Li(AlCl 4 )] · 3SO 2 , [Li 2 (SO 2 ) 8 ][B 12 Cl 12 ], [Na(AlCl 4 )] · 1.5SO 2 , Na 2 [B 12 Cl 12 ] · 4SO 2 , K 2 [B 12 F 12 ] · 6SO 2 Na[Me 3 NB 12 Cl 11 ] · SO 2, M 2 [B 12 Cl 12 ] · 8SO 2 (M = K + , Rb + ), Cs 2 [B 12 Cl 12 ] · SO 2 or [Mg(SO 2 ) 2 {AsF 6 } 2 ] . In these characterized compounds, however, exclusively coordination of SO 2 towards the metal centre was observed.…”