Dithionite Complexes

Dithionite does not act as a ligand in very many compounds. The structures of the complexes that do form are interesting insights into the bonding in dithionite (what orbital provides the pair of electons and what changes in bonding occur on complexation).

1. J. Organometal. Chem., 1975: Title: SYNTHESIS OF A TRANSITION METAL-DITHIONITE COMPLEX [pretty sketchy work but the first report] LINK2. J. Organometal. Chem., 1980: Title: SYNTHESIS, CHARACTERIZATION AND SOME REACTIONS OFORGANOMETALLIC COMPLEXES CONTAINING BRIDGNG DITHIONITE LIGAND [An extension of the previous publication to other metal systems] LINK 3. Organometallics, 1985: Title: Reduction of SO2 by (C5R5)M(C0)3H (M = Mo, W; R = H, Me).Chemistry and Structures of (C5H5)Nlo(CO),(SO,H),the FirstExample of Insertion of SO2 into a M-H Bond, and[ (C5M5,)Mo(CO)3],(S2O4),S-Bonded Dithionite Complex [Complex is described by authors as "unexpected" but still recovered in 31% yield, note the complex is to the C2h dithionite structure and the S-S distance is 3.692 A] LINK4. J. Amer. Chem. Soc., 1999: Title: Oxidation of the Sulfide Ligands to SO42- in the Dinuclear Complex{RuCl[P(OMe)3]2}2(µ-S2)(µ-Cl)(µ-N2H4): Synthesis andCharacterization of {RuCl[P(OMe)3]2}2(µ-S2)(µ-Cl)(µ-N2H4)+HSO4-,{RuCl2[P(OMe)3]2}2(µ-S)(µ-N2H4), and{RuCl[P(OMe)3]2}2(µ-S2O5)(µ-N2H4) [The dithionite complex is more of an intermediate than an isolated product but the mechanism is amusing] LINK

5. Angew. Chemie, 2006: Title: Direct Observation of Photochromic Dynamics in the Crystalline State of an Organorhodium Dithionite Complex [Nice work but a classic case of duplicate publication, the S-S distance is 2.330 A and note the energetic similarity of the S-S and S-O bonded dithionites] LINK and LINK

6. J. Organometal. Chem., 2007: Title: Synthesis and structural characterization of a photoresponsive organodirhodium complex with active S–S bonds:[(CpPhRh)2(l-CH2)2(l-O2SSO2)] (CpPh = g5-C5Me4Ph) [it may seem like a simple extension but these complexes are pretty remarkable, S-S in cis is 2.295 A and S-S in trans is 2.299 A, how is that possible?] LINK