Sulfinato

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... 

H202 to yield the corresponding sulfinate complex (553). In the latter, the sulfinato group is 0,0-bound—a very unusual coordination mode for Ni1 sulfinate complexes.1403... 

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... 

Die aus den Sulfenylchloriden durch Umsetzung mit Anilinen herstellbaren Sulfenylanilide lagern sich beim Behandeln mit alkoholischen Losungen von Natriumhydroxid zu den 2-Sulfinato-azobenzolen um1"3 ... 

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). 

Synthesis of Fluorinated Monomers through Sulfinato-Dehalogenation and Related Reactions Huang, W.-Y. Mavromol. Symp. 1994. 82. 67-75. 

Synthesis of Fluorinated Monomers through Sulfinato-Dehalogenation and Related Reactions ... 

Many Com(Con) complexes are photosensitive and cleavage of axial bonds to Co is induced by visible light.254,267 For alkyl, mercapto, sulfinato and selenocyanato Co111 corrins, homolytic fission (photoreduction) proceeds, whereas heterolytic dissociation (photoaquation) occurs for amino and cyano complexes. These photoprocesses are considered to be initiated by n -> n excitations. 

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... 

CM-MeS(0)2Mn(C0)4PPh3 as the isolable products however, structures of the respective O-sulfinato intermediates have not been determined. One cannot therefore rule out possible changes in geometry around the metal in two of the steps comprising the overall process. That rearrangements may have occurred is suggested by the reaction of SO2 with cis-MeMn(CO)4 CO which yields substantial tra f-MeS(0)2Mn(C0)4-in addition to the cis isomer (109). 

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