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|volume=4|page=235|year=1993|title=The Phenomenon of Conglomerate Crystallization in Coordination Compounds. XXIII: The Crystallization Behavior of ·2H<sub>2</sub>O (I) and of ·H<sub>2</sub>O (II)|doi=10.1007/BF00673698|s2cid=94847897 }}</ref>]] |volume=4|page=235|year=1993|title=The Phenomenon of Conglomerate Crystallization in Coordination Compounds. XXIII: The Crystallization Behavior of ·2H<sub>2</sub>O (I) and of ·H<sub>2</sub>O (II)|doi=10.1007/BF00673698|s2cid=94847897 }}</ref>]]


'''Transition metal sulfito complexes''' are ]s containing sulfite]] (SO32-) as a ligand. The inventory is large. Few sulfito complexes have commercial applications, but sulfite is a substrate for the molybdoenzyme sulfite oxidase.<ref>{{cite journal|doi=10.1021/cr020609d |title=Synthetic Analogues and Reaction Systems Relevant to the Molybdenum and Tungsten Oxotransferases |date=2004 |last1=Enemark |first1=John H. |last2=Cooney |first2=J. Jon A. |last3=Wang |first3=Jun-Jieh |last4=Holm |first4=R. H. |journal=Chemical Reviews |volume=104 |issue=2 |pages=1175–1200 |pmid=14871153 }}</ref> '''Transition metal sulfito complexes''' are ]s containing ] (SO<sub>3</sub><sup>2-</sup>) as a ]. The inventory is large. Few sulfito complexes have commercial applications, but sulfite is a substrate for the molybdoenzyme ].<ref>{{cite journal|doi=10.1021/cr020609d |title=Synthetic Analogues and Reaction Systems Relevant to the Molybdenum and Tungsten Oxotransferases |date=2004 |last1=Enemark |first1=John H. |last2=Cooney |first2=J. Jon A. |last3=Wang |first3=Jun-Jieh |last4=Holm |first4=R. H. |journal=Chemical Reviews |volume=104 |issue=2 |pages=1175–1200 |pmid=14871153 }}</ref>


==Bonding modes== ==Bonding modes==
In principle, sulfite can bond to metal ions via S or O. In this respect, sulfite as a ligand resembles ] ({{chem2|NO2-}}), which binds through N and O. S-bonded sulfites are more common than O-bonded sulfito ligands. In some cases, sulfite is a bridging ligand forming M-SO<sub>2</sub>-O-M’ linkages.<ref>{{cite journal|doi=10.1002/1099-0682(200112)2001:12<3067::AID-EJIC3067>3.0.CO;2-8 |title=Structural Investigations of Sulfite-Bridged Binuclear Complexes of Platinum(II) and Palladium(II) |date=2001 |last1=Krieglstein |first1=Roland |last2=Breitinger |first2=Dietrich K. |last3=Liehr |first3=Günther |journal=European Journal of Inorganic Chemistry |issue=12 |pages=3067–3072 }}</ref> In principle, sulfite can bond to metal ions via S or O. To some extent, the sulfito ligand resembles ] ({{chem2|NO2-}}), which can bind through N or O. Monodentate, ''S''-bonded sulfites are more common than O-bonded sulfito ligands. ''S''-Bonded sulfite is a ] with a strongly trans labilizing effect as indicated by the rapid ] of {{chem2|+}} to give {{chem2|+}}.<ref>{{cite journal |doi=10.1021/ja00964a063 |title=Substitution Reactions of Sulfitopentaamminecobalt(III) and Its Derivatives. Evidence for a Limiting SN1 Mechanism |date=1966 |last1=Halpern |first1=Jack |last2=Palmer |first2=Richard A. |last3=Blakley |first3=Lynne M. |journal=Journal of the American Chemical Society |volume=88 |issue=12 |pages=2877–2878 |bibcode=1966JAChS..88.2877H }}</ref>


In some cases, sulfite serves as a bridging ligand forming M-SO<sub>2</sub>-O-M’ linkages.<ref>{{cite journal|doi=10.1002/1099-0682(200112)2001:12<3067::AID-EJIC3067>3.0.CO;2-8 |title=Structural Investigations of Sulfite-Bridged Binuclear Complexes of Platinum(II) and Palladium(II) |date=2001 |last1=Krieglstein |first1=Roland |last2=Breitinger |first2=Dietrich K. |last3=Liehr |first3=Günther |journal=European Journal of Inorganic Chemistry |issue=12 |pages=3067–3072 }}</ref>
Sulfite has a strongly trans labilizing effect.


==Examples== ==Examples==
*{{chem2|ClO4}}<ref>{{cite journal|doi=10.1016/S0020-1693(00)81258-X |title=The Formation and reactivity of sulfito complexes of tetraethylenepentamine-cobalt(III): X-ray structure of αα-&#91;co(tetren)SO3&#93;ClO4 |date=1986 |last1=Schneider |first1=K.J. |last2=Van Eldik |first2=R. |last3=Roodt |first3=A. |last4=Leipoldt |first4=J.G. |journal=Inorganica Chimica Acta |volume=122 |pages=1–5 }}</ref> (tetren = {{chem2|HN(CH2CH2NHCH2CH2NH2)2}}) *{{chem2|+}}<ref>{{cite journal|doi=10.1016/S0020-1693(00)81258-X |title=The Formation and Reactivity of Sulfito Complexes of Tetraethylenepentamine-Cobalt(III): X-Ray Structure of αα-&#91;co(tetren)SO<sub>3</sub>&#93;ClO<sub>4</sub> |date=1986 |last1=Schneider |first1=K.J. |last2=Van Eldik |first2=R. |last3=Roodt |first3=A. |last4=Leipoldt |first4=J.G. |journal=Inorganica Chimica Acta |volume=122 |pages=1–5 }}</ref> (tetren = {{chem2|HN(CH2CH2NHCH2CH2NH2)2}})
*{{chem2|-}} (M = Rh, <ref>{{cite journal|doi=10.1107/S0108270185004504 |title=Sodium trans-bis(1,2-ethanediamine)disulfitorhodate(III) trihydrate, Na&#91;Rh(C2H8N2)2(SO3)2&#93;.3H2O |date=1985 |last1=Petrikowski |first1=G. |last2=Breitinger |first2=D. K. |journal=Acta Crystallographica Section C Crystal Structure Communications |volume=41 |issue=4 |pages=522–525 }}</ref> Co<ref>{{cite journal|doi=10.1071/CH9790291 |title=Crystal Structure of Disodium(I) cis-Bis(ethane-1,2-diamine)disulfitocobaltate(III) Perchlorate Trihydrate |date=1979 |last1=Raston |first1=CL |last2=White |first2=AH |last3=Yandell |first3=JK |journal=Australian Journal of Chemistry |volume=32 |issue=2 |page=291 }}</ref>, en = ]) *{{chem2|-}} (M = Rh,<ref>{{cite journal|doi=10.1107/S0108270185004504 |title=Sodium ''trans''-Bis(1,2-ethanediamine)disulfitorhodate(III) Trihydrate, Na&#91;Rh(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>2</sub>(SO<sub>3</sub>)<sub>2</sub>&#93;<sup>.</sup>3H<sub>2</sub>O |date=1985 |last1=Petrikowski |first1=G. |last2=Breitinger |first2=D. K. |journal=Acta Crystallographica Section C Crystal Structure Communications |volume=41 |issue=4 |pages=522–525 }}</ref> Co,<ref>{{cite journal|doi=10.1071/CH9790291 |title=Crystal Structure of Disodium(I) ''cis''-Bis(ethane-1,2-diamine)disulfitocobaltate(III) Perchlorate Trihydrate |date=1979 |last1=Raston |first1=CL |last2=White |first2=AH |last3=Yandell |first3=JK |journal=Australian Journal of Chemistry |volume=32 |issue=2 |page=291 }}</ref><ref>{{cite book |doi=10.1002/9780470132456.ch15 |title= Inorganic Syntheses |date=1973 |last1=Hargens |first1=Robert D. |last2=Min |first2=Woonza |last3=Henney |first3=Robert C. |chapter= Bis(ethylenediamine)sulfito Complexes of Cobalt(III) |volume=14 |pages=77–81 |isbn=978-0-470-13174-9 }}</ref> en = ])
*{{chem2|(2-)}} <ref>{{cite journal|doi=10.1002/zaac.19865390803 |title=Kristallstruktur und schwingungsspektrometrische Daten von cis-Na<sub>2</sub>&#91;Pd(SO<sub>3</sub>)<sub>2</sub>en&#93; · 4 H<sub>2</sub>O |date=1986 |last1=Breitinger |first1=D. K. |last2=Schottner |first2=G. |last3=Raidel |first3=M. |last4=Beck |first4=H. P. |journal=Zeitschrift für Anorganische und Allgemeine Chemie |volume=539 |issue=8 |pages=18–26 }}</ref> *{{chem2|(2-)}} <ref>{{cite journal|doi=10.1002/zaac.19865390803 |title=Kristallstruktur und Schwingungsspektrometrische Daten von ''cis''-Na<sub>2</sub>&#91;Pd(SO<sub>3</sub>)<sub>2</sub>en&#93;·4H<sub>2</sub>O |date=1986 |last1=Breitinger |first1=D. K. |last2=Schottner |first2=G. |last3=Raidel |first3=M. |last4=Beck |first4=H. P. |journal=Zeitschrift für Anorganische und Allgemeine Chemie |volume=539 |issue=8 |pages=18–26 }}</ref>
*{{chem2|-}} <ref>{{cite journal|doi=10.1107/S0567740875002828 |title=The Crystal and molecular structure of ethylenediammonium bis&#123; ''cis'' -&#91;ethylenediaminedisulphitoaurate(III)&#93;&#125; |date=1975 |last1=Dunand |first1=A. |last2=Gerdil |first2=R. |journal=Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry |volume=31 |issue=2 |pages=370–374 }}</ref> *{{chem2|-}} <ref>{{cite journal|doi=10.1107/S0567740875002828 |title=The Crystal and Molecular Structure of Ethylenediammonium bis&#123; ''cis'' -&#91;ethylenediaminedisulphitoaurate(III)&#93;&#125; |date=1975 |last1=Dunand |first1=A. |last2=Gerdil |first2=R. |journal=Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry |volume=31 |issue=2 |pages=370–374 |bibcode=1975AcCrB..31..370D }}</ref>


==Complexes with modified sulfito ligands== ==Complexes with modified sulfito ligands==
(3-)}}]] (3-)}}<ref name=H-bond/>]]
Being dibasic, sulfito ligands are susceptible to alkylation and protonation. Some examples: Being dibasic, sulfito ligands are susceptible to ''O''-alkylation and ''O''-protonation. Some examples:
*{{chem2|}}<ref>{{cite journal|doi=10.1021/ic00295a003 |title=(Polypyridine)ruthenium(II) complexes containing sulfite, bisulfite, and sulfur dioxide |date=1988 |last1=Allen |first1=L. R. |last2=Jeter |first2=D. Y. |last3=Cordes |first3=A. W. |last4=Durham |first4=B. |journal=Inorganic Chemistry |volume=27 |issue=22 |pages=3880–3885 }}</ref> *{{chem2|Ru(phen)2(SO3H)2}}<ref>{{cite journal|doi=10.1021/ic00295a003 |title=(Polypyridine)ruthenium(II) Complexes Containing Sulfite, Bisulfite, and Sulfur Dioxide |date=1988 |last1=Allen |first1=L. R. |last2=Jeter |first2=D. Y. |last3=Cordes |first3=A. W. |last4=Durham |first4=B. |journal=Inorganic Chemistry |volume=27 |issue=22 |pages=3880–3885 }}</ref>
*{{chem2|Pt(PPh3)2(SO3Me)2}}<ref>{{cite journal|doi=10.1007/BF00619056 |title=The crystal and molecular structure oftrans-Di(methylsulphito)bis-(triphenylphosphine)platinum(II) |date=1979 |last1=Hughes |first1=Glyn R. |last2=Minshall |first2=Peter C. |last3=Mingos |first3=D. Michael P. |journal=Transition Metal Chemistry |volume=4 |issue=3 |pages=147–150 }}</ref> *{{chem2|Pt2(SO3CH3)2}}<ref>{{cite journal|doi=10.1007/BF00619056 |title=The Crystal and Molecular Structure of ''trans''-Di(methylsulphito)bis-(Triphenylphosphine)platinum(II) |date=1979 |last1=Hughes |first1=Glyn R. |last2=Minshall |first2=Peter C. |last3=Mingos |first3=D. Michael P. |journal=Transition Metal Chemistry |volume=4 |issue=3 |pages=147–150 }}</ref>
*{{chem2|Pt2(en)2(mu\sS,O\sSO3)2}} <ref>{{cite journal|doi=10.1002/1099-0682(200112)2001:12<3067::AID-EJIC3067>3.0.CO;2-8 |title=Structural Investigations of Sulfite-Bridged Binuclear Complexes of Platinum(II) and Palladium(II) |date=2001 |last1=Krieglstein |first1=Roland |last2=Breitinger |first2=Dietrich K. |last3=Liehr |first3=Günther |journal=European Journal of Inorganic Chemistry |issue=12 |pages=3067–3072 }}</ref> unsym *{{chem2|Pt2(en)2(mu\sS,O\sSO3)2}} <ref>{{cite journal|doi=10.1002/1099-0682(200112)2001:12<3067::AID-EJIC3067>3.0.CO;2-8 |title=Structural Investigations of Sulfite-Bridged Binuclear Complexes of Platinum(II) and Palladium(II) |date=2001 |last1=Krieglstein |first1=Roland |last2=Breitinger |first2=Dietrich K. |last3=Liehr |first3=Günther |journal=European Journal of Inorganic Chemistry |issue=12 |pages=3067–3072 }}</ref>
*{{chem2|K3[PtCl2(SO3H)(SO3}}<ref>{{cite journal|doi= 10.1107/S0567740880009405 |title= Tripotassium ''cis'' -dichloro(hydrogendisulfito)platinate(II) K<sub>3</sub>&#91;Pt&#123;(SO<sub>3</sub>)<sub>2</sub>H&#125;Cl<sub>2</sub>&#93;. A case of an extremely short hydrogen bond O...H...O |date= 1980 |last1= Kehr |first1= W. G. |last2= Breitinger |first2= D. K. |last3= Bauer |first3= G. |journal= Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry |volume= 36 |issue= 11 |pages= 2545–2550 }}</ref> *{{chem2|(3-)}}<ref name=H-bond>{{cite journal|doi= 10.1107/S0567740880009405 |title= Tripotassium ''cis'' -dichloro(hydrogendisulfito)platinate(II) K<sub>3</sub>&#91;Pt&#123;(SO<sub>3</sub>)<sub>2</sub>H&#125;Cl<sub>2</sub>&#93;. A Case of an Extremely Short Hydrogen Bond O<sup>...</sup>H<sup>...</sup>O |date= 1980 |last1= Kehr |first1= W. G. |last2= Breitinger |first2= D. K. |last3= Bauer |first3= G. |journal= Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry |volume= 36 |issue= 11 |pages= 2545–2550 }}</ref>


==References== ==References==

Latest revision as of 06:53, 9 January 2025

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. 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(SO3)(NH3)5] to give [Co(SO3)(NH3)4(H2O)].

In some cases, sulfite serves as a bridging ligand forming M-SO2-O-M’ linkages.

Examples

  • [Co(tetren)SO3] (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(SO3H)(SO3)]

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

  • Ru(phen)2(SO3H)2
  • Pt[P(C6H5)3]2(SO3CH3)2
  • Pt2(en)2(mu−S,O−SO3)2
  • [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. 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. Bibcode:1966JAChS..88.2877H. doi:10.1021/ja00964a063.
  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. 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.
  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 Crystal Structure Communications. 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. Vol. 14. pp. 77–81. doi:10.1002/9780470132456.ch15. ISBN 978-0-470-13174-9.
  9. 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.
  10. 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. Bibcode:1975AcCrB..31..370D. doi:10.1107/S0567740875002828.
  11. ^ 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 OHO". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 36 (11): 2545–2550. doi:10.1107/S0567740880009405.
  12. 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.
  13. 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.
  14. 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:
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