Sulfinato complexes

Insertion of SO2 into the Fe—C bond in FelPorfCHi was first reported in 1982, giving the sulfinato complexes Fe(Por)S02CH2, which are moderately air stable but can be further oxidized by O2 to give the sulfonato complexes FelPorfSOiCH. " Alkyliron(Ill) porphyrins insert CO to give the acyl complexes Fe(Por)C(0)R. For example, Fe(TPP)C(0)-n-Bu was formed either by this method or by the reaction of I Fe(TPP) r with ClC(0)-/ -Bu, and was characterized by an X-ray crystal structure... 

O-sulfinato complex, 37 287 sulfito complexes, 37 293 sulfur, selenium, and tellurium tetrahal-ide complexes, 37 299 thiocyanato complexes, 37 264 thioether and selenoether complexes, 37 288... 

Sodium sulfinates NaRS02 (R = Me, Ph or MeC6H4) reacted in ethanol with VC13 and trisfO, O -sulfinato) complexes were obtained.264 The IR spectra are consistent with the sulfinato ions as bidentate. The electronic spectra show two d-d transitions v3 in the range... 

S-bonded alkyl and aryl sulfinato complexes can be prepared by the reaction of sulfonyl chlorides with Pt(C2H4)(PPh3)2,1633 the phase-catalyzed reaction of PtCl with NaS02R, 4 or the insertion of S02 into a platinum-alkyl bond1635 as shown in equations (481)-(483). When PtCl(S02R)L2 is treated with silver ion the 0,0 -bonded chelate complex (173) is formed (equation 484). 

Table 71 Preparations Some S-Bonded Sulfito, Sulfinato Complexes of Cobalt(IlI) (Monodentate)... 

There remain a number of other five-coordinate complexes whose physical properties are shown in Table 66. Of these complexes only the AsCy3 complex has been prepared from a rhodium(III) source (equation 194). The remainder have been prepared from oxidative addition reactions of [RhCl(PPh3)3], The arylazo complexes have structure (75),948 whilst the sulfinato complexes are bound through sulfur.950... 

The complexes of this stoichiometry containing ditertiary arsines probably outnumber those of tertiary phosphines. They have been prepared by the same general methods as the tertiary phosphine complexes, although unusually [RhCl2(diars)2]Cl has been prepared from Na3[RhCl6]. Despite the relative antiquity of this method,1044 it has not been generally adopted (equation 251). The physical properties of the ditertiary arsine complexes are listed in Table 82. It may be noted that the IR spectra of the sulfinato complexes indicate that these are S-bonded like their phosphorus analogs.230... 

The 0-sulfinato complex corresponds to the 1,2-insertion. Transition metal complexes in a relatively low oxidation state usually yield S-sulfinato derivatives, whereas the 0-sulfinato complexes are obtained with alkyl and aryl complexes of nontransition cations, such as zinc(II) or tin(II) . 

In a competitive experiment, AuMe2Ph(PMe3) reacted with sulfur dioxide and gave the following S-sulfinato complex ... 

The presumably weaker gold-methyl bond is preferentially cleaved, consistent with a primary attack by sulfur dioxide, followed by methyl migration . The 2,2 -dipyridyl sulfinato complexes of iron(II), of formula Fe(2,2 -CioH8N2)2[OS(0)R]2, undergo an irreversible transformation into the thermodynamically stable S-sulfinato derivatives Fe(2,2 -CioHsN2)2[S(02)R]2 by refluxing in pyridine . 

On the other hand, the cyclopentadienyl derivatives of iron(II), Fe(rj -CsH5)R(CO)2, molybdenum(II), Mo(r -C5H5)R(CO)3, and MR(CO)5, M = Mn, Re, react with sulfur dioxide giving initially the 0-sulfinato complexes, which then rearrange to the S-bonded linkage isomers . ... 

In many transition metal complexes, geometrical and linkage isomerization reactions involve ligand substitution processes. One example of a photoin-duced linkage isomerization reaction, namely, the isomerization from an S-to an O-bonded sulfinato complex, Co(en)2(S02CH2CH2NH2)2+, has been studied as a function of pressure. The O-bonded product undergoes a thermal back reaction to the S-bonded complex and this system, shown in... 

S-bonded alkyl and aryl sulfinato complexes can be prepared by the reaction of sulfonyl... 

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