Chemistry:Transition metal sulfito complex

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The structure of [Co(ethylenediamine)2(SO3)N3]. Color code: blue = N, red = O, yellow = S.[1]

Transition metal sulfito complexes are coordination compounds containing sulfite (SO2−
3) as a ligand. Many examples have been characterized. Few sulfito complexes have commercial applications, but sulfite is a substrate for the molybdoenzyme sulfite oxidase.[2]

Bonding modes

In principle, sulfite can bond to metal ions via S or O. To some extent, the sulfito ligand resembles nitrito (NO−
2), which can bind through N or O. Monodentate, S-bonded sulfites are more common than O-bonded sulfito ligands. S-bonded sulfite is a soft ligand with a strongly trans labilizing effect as indicated by the rapid aquation of [Co(SO
3)(NH
3)
5]+
 to give [Co(SO
3)(NH
3)
4(H
2O)]+
.[3]

Sulfite can function as a bridging ligand. One example is Pt
2(en)
2(μ–−
SO
3)
2 (en = ethylenediamine)[4]

In some cases, sulfite simply serves as an anion. An example is the hexaaquo complex [Ni(H2O)6]SO3.[5]

Preparation

Sulfito complexes are typically prepared by substitution of metal complexes with sodium sulfite. The method is illustrated by the syntheses of the octahedral rhodium(III) and cobalt(III) complexes [M(SO
3)
2(en)
2]−
 (M = Rh,[6] Co),[7][8] (where en = ethylenediamine). Some metal-sulfur dioxide complexes react with aqueous base to give sulfito derivatives:[9]

[Ru(NH
3)
4(OH
2)(SO
2)]2+ + OH−
 ⇌ [Ru(NH
3)
4(OH
2)(SO
3H)]+

Examples

  • [Co(tetren)SO
    3    ]+
    , octahedral cobalt(III) bound also to a pentadentate amine[10] (tetren = HN(CH
    2    CH
    2    NHCH
    2    CH
    2    NH
    2    )
    2    )
  • [Pd(en)(SO
    3    )
    2    ]2−    , square planar palladium(II)[11]
  • [Au(en)(SO
    3    )
    2    ]−
    , square planar gold(III)[12]
  • [Pt
    3    S
    2    (SO
    3    )
    6    ]10−    , illustrating a rare anion with a –10 charge consisting of three square planar platinum(II) centers[13]
  • [Co(NH
    3    )
    5    SO
    3    ]+
    Cl−
     where the Co-N bond trans to S is 205.5 pm in length, and Co-N bonds cis to S are 196 pm, ca. 5% shorter. This difference illustrates the high trans influence exerted by the sulfito ligand.[14]

Complexes with modified sulfito ligands

Structure of [PtCl
2(SO
3H)(SO
3)]3−[15]

Being dibasic, sulfito ligands are susceptible to O-alkylation and O-protonation. Some examples of such complexes:

  • Ru(phen)
    2    (SO
    3    H)
    2    [16]
  • Pt[P(C
    6    H
    5    )
    3    ]
    2    (SO
    2    (OCH
    3    ))
    2    [17]
  • [PtCl
    2    (SO
    3    H)(SO
    3    )]3−    [15]

References

  1. ↑ I. Bernal; J. Cetrullo; W. G. Jackson (1993). "The Phenomenon of Conglomerate Crystallization in Coordination Compounds. XXIII: The Crystallization Behavior of [cis-Co(en)2(N3)(SO3)]·2H2O (I) and of [cis-Co(en)2(NO2)(SO3)]·H2O (II)". Struct. Chem. 4: 235. doi:10.1007/BF00673698. 
  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. ↑ Halpern, Jack; Palmer, Richard A.; Blakley, Lynne M. (1966). "Substitution Reactions of Sulfitopentaamminecobalt(III) and Its Derivatives. Evidence for a Limiting SN1 Mechanism". Journal of the American Chemical Society 88 (12): 2877–2878. doi:10.1021/ja00964a063. Bibcode: 1966JAChS..88.2877H. 
  4. ↑ 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. 
  5. ↑ Baggio, S.; Becka, L.N. (1969). "A reinvestigation of the structure of nickel sulphite hexahydrate, NiSO3(H2O)6". Acta Crystallographica, Section B B25 (6): 1150-1155. doi:10.1107/S0567740869003657. Bibcode: 1969AcCrB..25.1150B. 
  6. ↑ 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 41 (4): 522–525. doi:10.1107/S0108270185004504. 
  7. ↑ 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. 
  8. ↑ Hargens, Robert D.; Min, Woonza; Henney, Robert C. (1973). "Bis(ethylenediamine)sulfito Complexes of Cobalt(III)". Inorganic Syntheses. 14. pp. 77–81. doi:10.1002/9780470132456.ch15. ISBN 978-0-470-13174-9. 
  9. ↑ Isied, Stephan; Taube, Henry (1974). "Effects of Sulfur dioxide, bisulfite(1−), and sulfite(2−) as auxiliary ligands on the reactivity of ammineruthenium(II)-ligand bonds". Inorganic Chemistry 13 (7): 1545–1551. doi:10.1021/ic50137a001. 
  10. ↑ 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. 
  11. ↑ Breitinger, D. K.; Schottner, G.; Raidel, M.; Beck, H. P. (1986). "Kristallstruktur und Schwingungsspektrometrische Daten von cis-Na2[Pd(SO3)2en]·4H2O". Zeitschrift für Anorganische und Allgemeine Chemie 539 (8): 18–26. doi:10.1002/zaac.19865390803. 
  12. ↑ Dunand, A.; Gerdil, R. (1975). "The Crystal and Molecular Structure of Ethylenediammonium bis{cis-[ethylenediaminedisulphitoaurate(III)]}". Acta Crystallographica, Section B 31 (2): 370–374. doi:10.1107/S0567740875002828. Bibcode: 1975AcCrB..31..370D. 
  13. ↑ Rajan, Ananthu; Elcheikh Mahmoud, Mahmoud; Wang, Fei; Bhattacharya, Saurav; Mougharbel, Ali S.; Ma, Xiang; Müller, Anja B.; Nisar, Talha et al. (2022). "Discovery of Polythioplatinate(II) [Pt3S2(SO3)6]10– and Study of Its Solution and Catalytic Properties". Inorganic Chemistry 61 (30): 11529–11538. doi:10.1021/acs.inorgchem.2c00777. PMID 35866749. 
  14. ↑ Elder, R. C.; Heeg, Mary Jane; Payne, M. Diane; Trkula, Mitchell; Deutsch, Edward (1978). "Trans effect in octahedral complexes. 3. Comparison of kinetic and structural trans effects induced by coordinated sulfur in sulfito- and Sulfinatopentaaminecobalt(III) complexes". Inorganic Chemistry 17 (2): 431–440. doi:10.1021/ic50180a048. 
  15. ↑ 15.0 15.1 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 36 (11): 2545–2550. doi:10.1107/S0567740880009405. 
  16. ↑ 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. 
  17. ↑ Hughes, Glyn R.; Minshall, Peter C.; Mingos, D. Michael P. (1979). "The Crystal and Molecular Structure of trans-Di(methylsulphito)bis-(Triphenylphosphine)platinum(II)". Transition Metal Chemistry 4 (3): 147–150. doi:10.1007/BF00619056. 



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