Transition metal complexes of sulfur monoxide

Transition metal complexes of sulfur monoxide refers to coordination complexes with sulfur monoxide (SO) as a ligand. The topic is relevant to the metal-promoted redox reactions of sulfur and sulfur oxides. Sulfur monoxide is unstable in condensed form, so its complexes are almost always prepared indirectly, e.g., using reagents that release SO.

Bonding modes

SO can bond to metals in a number ways:[2][3]

  • a terminal ligand, with a bent M−S−O arrangement, analogous structurally to "bent" nitrosyl. In such cases, SO is a Lewis base. An example is IrCl(P(i-Pr)3)2(SO) (i-Pr = isopropyl).[4]
  • triply bridging as in Fe3(μ3-S)(μ3-SO)(CO)9. In such cases SO is a 4-electron donor.
  • Bridging with the μ-η1,η1-SO motif.[5] Another bridging mode is μ-η1,η2-SO, as observed in some Rh2 complexes.[6]

Complexes with the M−O−S arrangement have been observed using the techniques of laser ablation and low temperature spectroscopy.[7][8]

Synthesis

SO complexes can be prepared from ethylene episulfoxides. This heterocycle binds metals through S, then releases ethylene.[2] Lewis acid adducts of sulfinylamines release SO when heated. In this way [RhCl(SO)(PPh3)2]2 can be produced from RhCl(PPh3)3 (Ph = C6H5).[9]

Another approach involves redox reactions of metal sulfides. Some cases involve well-defined oxidants such as peroxides. In other cases, air is assumed to be the oxidant.[5]

References

  1. ^ Karet, G. B.; Stern, C. L.; Norton, D. M.; Shriver, D. F. (1993). "Synthesis and Reductive Sulfur-Oxygen Cleavage of Sulfur Oxide Clusters: [PPN][HFe3(CO)9SO2] and [PPN]2[Fe3(CO)9SO]". Journal of the American Chemical Society. 115 (22): 9979–9985. Bibcode:1993JAChS.115.9979K. doi:10.1021/ja00075a014.
  2. ^ a b Schenk, W. A. (1987). "Sulfur Oxides as Ligands in Coordination Compounds". Angewandte Chemie International Edition in English. 26 (2): 98–109. doi:10.1002/anie.198700981.
  3. ^ Woollins, J. D. (1995). "Sulfur: Inorganic Chemistry". Encyclopedia of Inorganic Chemistry. John Wiley and Sons. ISBN 0-471-93620-0.
  4. ^ Schenk, Wolfdieter A.; Leissner, Johanna; Burschka, Christian (1984). "Stabilization of Sulfur Monoxide by Coordination to Transition Metals". Angewandte Chemie International Edition in English. 23 (10): 806–807. doi:10.1002/anie.198408061.
  5. ^ a b Arikawa, Yasuhiro; Yamada, Motoki; Takemoto, Nobuko; Nagaoka, Takuya; Tsujita, Yusuke; Nakamura, Taiji; Tsuruta, Yusuke; Horiuchi, Shinnosuke; Sakuda, Eri; Yoshizawa, Kazunari; Umakoshi, Keisuke (2023). "Stepwise Sulfite Reduction on a Dinuclear Ruthenium Complex Leading to Hydrogen Sulfide". Journal of the American Chemical Society. 145 (40): 21729–21732. Bibcode:2023JAChS.14521729A. doi:10.1021/jacs.3c07248. PMID 37650604.
  6. ^ Bianchini, Claudio; Mealli, Carlo; Meli, Andrea; Sabat, Michal (1985). "Stepwise Metal-Promoted Conversion of η2-CS2 into η2-SO. Synthesis and Crystal Structure of the Complex [(triphos)Rh(µ-SO)2Rh(triphos)][BPh4]2·HCONMe2 [triphos = MeC(CH2PPh2)3]". J. Chem. Soc., Chem. Commun. (15): 1024–1025. doi:10.1039/C39850001024.
  7. ^ Wei, R.; Chen, X.; Gong, Y. (2019). "End-On Oxygen-Bound Sulfur Monoxide Complex of Titanium Oxyfluoride". Inorganic Chemistry. 58 (17): 11801–11806. doi:10.1021/acs.inorgchem.9b01880. PMID 31441297. S2CID 201617509.
  8. ^ Wei, R.; Chen, X.; Gong, Y. (2019). "Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides". Inorganic Chemistry. 58 (6): 3807–3814. doi:10.1021/acs.inorgchem.8b03411. PMID 30707575. S2CID 73438027.
  9. ^ Longobardi, Lauren E.; Wolter, Vanessa; Stephan, Douglas W. (2015). "Frustrated Lewis Pair Activation of an N -Sulfinylamine: A Source of Sulfur Monoxide". Angewandte Chemie International Edition. 54 (3): 809–812. Bibcode:2015ACIE...54..809L. doi:10.1002/anie.201409969. PMID 25376102.
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