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Transition metal sulfito complex

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The structure of . Color code: blue = N, red = O, yellow = S.

Transition metal sulfito complexes are coordination compounds containing sulfite (SO3) as a ligand. The inventory is large. Few sulfito complexes have commercial applications, but sulfite is a substrate for the molybdoenzyme sulfite oxidase.

Bonding modes

In principle, sulfite can bond to metal ions via S or O. In this respect, sulfite as a ligand resembles nitrite (NO−2), which can bind through N or O. Monodentate, S-bonded sulfites are more common than O-bonded sulfito ligands. In some cases, sulfite is a bridging ligand forming M-SO2-O-M’ linkages.

Sulfite has a strongly trans labilizing effect.

Examples

  • [Co(tetren)SO3]ClO4 (tetren = HN(CH2CH2NHCH2CH2NH2)2)
  • [M(SO3)2(en)2] (M = Rh, Co, en = ethylenediamine)
  • [Pd(en)(SO3)2]
  • [Au(en)(SO3)2]

Complexes with modified sulfito ligands

Structure of PtCl2(SO3)2H]

Being dibasic, sulfito ligands are susceptible to alkylation and protonation. Some examples:

  • [Ru(phen)2(SO3H)2]
  • Pt(PPh3)2(SO3Me)2
  • Pt2(en)2(mu−S,O−SO3)2 unsym
  • K3[PtCl2(SO3H)(SO3

References

  1. I. Bernal; J. Cetrullo; W. G. Jackson (1993). "The Phenomenon of Conglomerate Crystallization in Coordination Compounds. XXIII: The Crystallization Behavior of ·2H2O (I) and of ·H2O (II)". Struct. Chem. 4: 235. doi:10.1007/BF00673698. S2CID 94847897.
  2. Enemark, John H.; Cooney, J. Jon A.; Wang, Jun-Jieh; Holm, R. H. (2004). "Synthetic Analogues and Reaction Systems Relevant to the Molybdenum and Tungsten Oxotransferases". Chemical Reviews. 104 (2): 1175–1200. doi:10.1021/cr020609d. PMID 14871153.
  3. Krieglstein, Roland; Breitinger, Dietrich K.; Liehr, Günther (2001). "Structural Investigations of Sulfite-Bridged Binuclear Complexes of Platinum(II) and Palladium(II)". European Journal of Inorganic Chemistry (12): 3067–3072. doi:10.1002/1099-0682(200112)2001:12<3067::AID-EJIC3067>3.0.CO;2-8.
  4. Schneider, K.J.; Van Eldik, R.; Roodt, A.; Leipoldt, J.G. (1986). "The Formation and reactivity of sulfito complexes of tetraethylenepentamine-cobalt(III): X-ray structure of αα-[co(tetren)SO3]ClO4". Inorganica Chimica Acta. 122: 1–5. doi:10.1016/S0020-1693(00)81258-X.
  5. Petrikowski, G.; Breitinger, D. K. (1985). "Sodium trans-bis(1,2-ethanediamine)disulfitorhodate(III) trihydrate, Na[Rh(C2H8N2)2(SO3)2].3H2O". Acta Crystallographica Section C Crystal Structure Communications. 41 (4): 522–525. doi:10.1107/S0108270185004504.
  6. Raston, CL; White, AH; Yandell, JK (1979). "Crystal Structure of Disodium(I) cis-Bis(ethane-1,2-diamine)disulfitocobaltate(III) Perchlorate Trihydrate". Australian Journal of Chemistry. 32 (2): 291. doi:10.1071/CH9790291.
  7. Breitinger, D. K.; Schottner, G.; Raidel, M.; Beck, H. P. (1986). "Kristallstruktur und schwingungsspektrometrische Daten von cis-Na2[Pd(SO3)2en] · 4 H2O". Zeitschrift für Anorganische und Allgemeine Chemie. 539 (8): 18–26. doi:10.1002/zaac.19865390803.
  8. Dunand, A.; Gerdil, R. (1975). "The Crystal and molecular structure of ethylenediammonium bis{ cis -[ethylenediaminedisulphitoaurate(III)]}". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 31 (2): 370–374. doi:10.1107/S0567740875002828.
  9. ^ Kehr, W. G.; Breitinger, D. K.; Bauer, G. (1980). "Tripotassium cis -dichloro(hydrogendisulfito)platinate(II) K3[Pt{(SO3)2H}Cl2]. A case of an extremely short hydrogen bond O...H...O". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 36 (11): 2545–2550. doi:10.1107/S0567740880009405.
  10. Allen, L. R.; Jeter, D. Y.; Cordes, A. W.; Durham, B. (1988). "(Polypyridine)ruthenium(II) complexes containing sulfite, bisulfite, and sulfur dioxide". Inorganic Chemistry. 27 (22): 3880–3885. doi:10.1021/ic00295a003.
  11. Hughes, Glyn R.; Minshall, Peter C.; Mingos, D. Michael P. (1979). "The crystal and molecular structure oftrans-Di(methylsulphito)bis-(triphenylphosphine)platinum(II)". Transition Metal Chemistry. 4 (3): 147–150. doi:10.1007/BF00619056.
  12. Krieglstein, Roland; Breitinger, Dietrich K.; Liehr, Günther (2001). "Structural Investigations of Sulfite-Bridged Binuclear Complexes of Platinum(II) and Palladium(II)". European Journal of Inorganic Chemistry (12): 3067–3072. doi:10.1002/1099-0682(200112)2001:12<3067::AID-EJIC3067>3.0.CO;2-8.
Coordination complexes
H donors:
B donors:
C donors:
Si donors:
N donors:
P donors:
O donors:
S donors:
Halide donors:
Categories: