Thiophenolate complex

Lover T efa/1997 Electrospray mass spectrometry of thiophenolate-capped clusters of CdS, CdSe and ZnS and cadmium and zinc thiophenolate complexes observation of fragmentation and metal, chalcogenide and ligand exchange processes Inorg. Chem. 36 3711... 

With OH and SH, the nucleophilic substitution of Cl has been reported. Thus, with NaOH, there is a report of successful nucleophilic substitution in 50% aq. acetone at room temperature to give the phenol complex in 36% yield. The latter is then spontaneously deprotonated to give the cyclohexadienyl complex (Eq. (24)). An identical reaction was carried out using NaSH in MeCN (50% yield) to give the thiophenol complex which was deprotonated [72] Eq. (25). These reactions would be especially valuable because direct synthesis of the phenol or thiophenol complexes from ferrocene is not possible due to the strong interaction between the heteroatom and A1C13 [11, 19]. Recent improvement and use of this reaction were achieved [88],... 

The bi- and tridentate phosphines dppp (l,3-bis(diphenylphosphino)propane) and dppep (bis (2-diphenylphosphinoethyl)phenylphosphine) have been complexed with Co and their divalent four- and five-coordinated thiophenolate complexes Co(dppp)(SPh)2 and Co(dppep)(SPh)2 have been isolated and structurally characterized.379 Somewhat related to dppp is the bidentate silane Ph2PCH2SiMe2CH2PPh2, which forms high-spin, pseudo-tetrahedral dihalocobalt(II) complexes.380... 

Thiophenolate complexes have been discussed, however, a considerable amount of alkylthiolate zinc chemistry is also known. The zinc alkylthiolate complexes with methanethiolate, ethanethiolate, and /. so-propylthiolate have been synthesized and characterized as precursors for ZnS formation. Thermolysis studies demonstrated the formation of ZnS and release of dimethylsulfide. Reactivity was similar with only the rm-propyl derivative showing much slower reaction.523 The polyzincate Zni0S4(SEt)i2L4 is a well-characterized neutral zinc sulfur compound.524... 

Polymer formation is still observed with some sterically hindered thiolates, 2,4,6-Ao-propyl thiophenolate, and 2,4,6-trimethyl thiophenolate complexes have been studied. They can be synthesized by the reaction of Zn[N(SiMe3)2]2 with the appropriate arene chalcogenol. With the least steric bulk, the trimethyl derivative forms coordination polymers that can only be dissolved in strongly coordinating solvents. The iso-propyl derivative is more soluble forming oligomers in solution. 1... 

It is well-established that the molecular and electronic structures of metal complexes of azamacrocycles are greatly affected upon N-alkylation (197). This is mainly due to two factors (a) the decrease of the ligand field strength and (b) the increase in the steric requirements upon going from a secondary to a tertiary amine donor function (251). To examine whether the properties of the dinuclear amine-thiophenolate complexes are affected by the N-alkyl substituents, analogous complexes of the... 

L0ver, T. Bowmaker, G.A. Henderson, W. Cooney, R.P. ESl-MS of Some Cadmium Thiophenolate Complexes and of a Thiophenolate Capped CdS Cluster. Chem. Commun. 1996, 683-685. 

As a mimic of the well-studied galactose oxidase [37], a copper(II) thiophenol complex catalyzes the oxidation of primary alcohols to aldehydes in the presence of (Scheme 12) [38]. The latter also promotes the oxidation of secondary alcohols to diols (Scheme 12). The catalytic cycle starts with the oxidation of copper by O, leading to a biradical species. The intermediate 39 is produced from 38 by coordination of two alkoxide substrates. The rate-limiting step is the formation of 40 from 39 by a hydrogen atom transfer from the secondary alcoholate to the oxygen-centered radicals of the aminophenols ligands. The cycle is then closed by radical dimerization which leads the formation of the diol [39]. 

The benzenethiolato ligand has been coordinated to a rhodium center in the complex Rh(SPh)[P(CH3)3]3. This complex, prepared from sodium thiophenolate and Rh(Cl)[P(CH3)3]3, reacts smoothly with air either in the solid state or in solution (155) to form the yellow dioxygen complex Rh(02)(SPh)[P(CH3)3]3. In a similar fashion, a mixture of Rh[P(CH3)3]4HCl and the thiophenolate ion reacts with air in solution to form the dioxygen complex The analogous complex with para-methoxythiophenolate can also be formed in this manner. Although the mechanism of formation of the dioxygen complexes directly from the thiophenolate anion and Rh[P(CH3)3]4 Cl is not fully understood, the initial formation of a rhodium(I)-thiophenolato complex such as Rh(SR)[P(CH3)3l , n = 3 or 4, is possible the extreme sensitivity of the intermediate thiophenolate complex prevented its isolation. 

The character of the coordinated catechols has been studied by Mossbauer spectroscopy [38]. Since the value of A is a measure of the hyperfine interaction of the iron electron with Fe, it reflects the covalency of the metal-ligand bands. The value of A/gnPn for the catechol complex is -18.9 T, that is the smallest observed for a dioxygenase complex -20.8 T for the phenol complex and -20.0 T for the thiophenol complex. The lowest values are explained by a greater delocalization of unpaired spin density away from the ferric center onto the catechol, generating a radical character of the catechol. The unpaired spin density delocalization is consistent with the paramagnetic shifts of protons of the catecholate ligand observed by NMR. 

A) Four-coordinate [Fe(2,3,5,6-tetramethylphenolate)4]% five-coordinate Fe(saloph)catH, six-coordinate [Fe(salen)cat] (B) iron-ovotransferrin-carbonate complex, protocatechuate 3,4-dioxygenase-succinate complex, catechol 1,2-dioxygenase-thiophenolate complex [59]. 

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