Thiolato ligands

Ferrocene compounds containing heteroelements are versatile building blocks for polynuclear complexes. They possess electrochemically active iron centers as well as unique cylindrical shapes. An example of ferrocene-substituted thiolato ligands is l,l -ferrocenedithiolate (S2fc). Its complex with Pd(II) lacks a Pd—Fe bond. 

The first examples of DNA metallointercalators containing a 1,2- or 1,7-carborane thiolato ligand have been reported.349 For example, treatment of [Pt(OTf)(terpy)]+ (terpy = 2,2 6, 2 -terpyr-idine) with l-HSCH2-l,2-C2B10Hii leads to the formation of [Pt(l-SCH2-l,2-C2BioHn)(terpy)]+ (143). The DNA-binding properties of several complexes have also been described. 

In conclusion, the presented dinuclear iron structure is the first example of a bio-mimetic iron compound, which can be regarded as a first generation model for the class of [Fe]-only hydrogenases. The complex incorporates both relevant carbon monoxide ligands, as well as three bridging thiolato ligands, which could be possibly present in the active site of these enzymes. 

Approximate square plane about Pd. Non-bridging pentafluorobenzene-thiolato ligands are trans. 

Platinum(II) thiolates can be decomposed in strong acid because of protonation at sulfur (equation 509). This reaction is similar to electrophilic alkylation at the coordinated thiolate, although in this case the thioether complex may be isolable (equation 510). Thiolato ligands are unreactive to nucleophiles, and only under the most forcing conditions does ligand replacement occur. 

Mononuclear Mov complexes with sterically hindered monodentate thiolato ligands are of interest as models for special molybdenum enzymes (the Mo oxidases). Here dimer formation via thiolato bridges and sulfide formation by C—S bond cleavage do not occur. Such a ligand is TIPTH. The complex [Mo(CO)2(TIPT)3) (14), with essentially trigonal prismatic coordination about Mo and trans CO groups in the axial sites, can be obtained.91... 

Wagenknecht H-A, Claude C, Woggon W-D (1998) New Enzyme Models of Chloroperoxidase Improved Stability and Catalytic Efficiency of Iron Porphyrinates Containing a Thiolato Ligand. Helv Chim Acta 81 1506... 

Heinrich L, Li Y, Vaissermann J, Chottard J-C (2001) A bis(carboxamido-N)diisocyanidobis (sulfenato-S)cobalt(HI) complex, model for the post-translational oxygenation of nitrile hydratase thiolato ligands. Eur J Inorg Chem 1407-1409... 

Han Y-F, Lin Y-J, Jia W-G, Jin G-X (2009) Half-sandwich Ir-based neutral organometallic macrocycles containing pyridinc-4-thiolato ligands. Dalton Trans 2077-2080... 

Wagenknecht HA, Claude C, Woggon WD (1998) New enzyme models of chloroperoxidase improved stability and catalytic efficiency of iron porphyrinates containing a thiolato ligand. Helv Chim Acta 81 1506-1520... 

A thiolato-nitrosyl complex [Re2 (NO)2 (SPh)7] has been made in low yield by reacting [Re(NO)Cl2(PPh3)2] (later reformulated as [Re(NO)Cl2(OMe)(PPh3)2])560,561 with thiophenol in refluxing methanol in the presence of triethylamine. The crystal structure performed on the [Pl P] salt of the p-tolylthiol derivative shows the complex to consist of two pseudooctahedral rhenium units linked by three bridging thiolato ligands. The Re—Re distance of 2.783(1) A indicates significant metal-metal interaction.562... 

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