Synthesis and Structure of [Ni(SO₂)₆](AsF₆)₂ and [Fe(SO₂)₄(FAsF₅)₂]

Abstract

Six η1‐O‐coordinated SO2 ligands are present in the pinwheel‐shaped cation of complex 1. This mode of coordination was considered unusual. The synthesis was achieved by oxidation of Ni powder with AsF5 in liquid SO2. An analogous reaction with iron yielded m‐[Fe(SO2)4(FAsF5)2].

Crown Ether Complexes of Alkali‐Metal Chlorides from SO2

“…[5] S-( e.g.,[ Mn(C 5 H 5 )(CO 2 )(SO 2 )]) [6] and S,O-coordination (e.g.,[ Mo(CO) 3 (phen)(SO 2 )],p hen = phenanthroline) [7] were observed for electron-rich complexes. [8] O-( e.g.,[ Ni(SO 2 ) 6 ] [AsF 6 ] 2 ) [9] and bridging m-O,O'-coordination (e.g.,[ Li(OSO) 6/2 ] [AlCl 4 ] [10] was reported for hard d-and f-block elements and main-group metal atoms. Thel atter require the presence of almost non-coordinating anions, [11] such as [B 12 Cl 12 ] 2À , [12][13][14] [AsF 6 ] À [15] or [Al{OC(CF 3 ) 3 } 4 ] À , [16] to provide sufficients olubility for the correspondings alts.…”

Cooperative Binding of SO2 under M–O and C–S Bond Formation in a Rhenium(I) Complex with Activated Amino- or Iminopyridine Ligand

“…Specifically, SO 2 can act as an ambiphilic ligand: The η 1 - S coordination mode to a metal center can be governed by electron donor (L-type) or electron acceptor (Z-type ligand) properties through the same sulfur atom. Each scenario is characterized by a distinct geometry, that is, a coplanar or pyramidal arrangement, respectively (Scheme , (I) A,B). , In addition, the η 1 - O (C) , and η 2 - S,O coordination modes are observed (D). − Stephan, Erker, Grimm, and co-workers reported the activation of SO 2 by frustrated Lewis acid/base pairs (FLPs) under concomitant P–S and B–O bond formation (Scheme , (II)). , Recent reports concerning the activation of SO 2 include uranium­(III) compounds, which allow for the formation of sulfite and dithionite complexes as well as the reaction of SO 2 and decamethylmetallocenes. , Herein, we report on an unusual binding mode of SO 2 triggered by metal–ligand cooperation (MLC), where both the transition metal center and a iminopyridine-based C-nucleophilic actor ligand participate in the activation of SO 2 via M–O and C–S bond formation (Scheme , (III)). MLC in transition metal complexes involving pyridine-based ligands was developed into an important tool in bond-activation chemistry. − Along these lines, we recently described an anionic Re­(I) triscarbonyl complex, which includes a redox active bidentate amidopyridine ligand (K­[Re­( amidopy )­(CO) 3 ] (Scheme , 1 ).…”