Generation of Thiosulfate, Selenite, Dithiosulfite, Perthionitrite, Nitric Oxide, and Reactive Chalcogen Species by Binuclear Zinc(II)-Chalcogenolato/-Polychalcogenido Complexes.

A comparative bioinspired reactivity study of new binuclear Zn(II) complexes featuring coordinated thiolate, selenolate, trisulfide and diselenide in relation with (i) the generation of reactive sulfur/selenium species (RSS/RSeS), (ii) the oxygen dependent oxidation and disproportionation of polysulfide (Sn2-) to produce sulfite (SO32-), thiosulfate (S2O32-) and sulfide (S2-) by sulfur oxygenase reductase (SOR), and (iii) the reaction of Sn2- with nitrite (NO2-) to generate thionitrite (SNO-), perthionitrite (SSNO-) and nitric oxide (NO), is presented. The binuclear Zn(II)-thiolate/selenolate complexes could react with elemental sulfur to generate RSS/RSeS while similar reactions involving elemental selenium could not generate RSeS. The dizinc(II)-S3 and the dizinc(II)-Se2 complexes could react with dioxygen (O2) to generate binuclear Zn(II) complexes featuring coordinated thiosulfate (S2O32-) and selenite (SeO32-), respectively. Finally, unlike the nonreactive nature of the dizinc(II)-Se2 complex toward NO2-, reaction of the dizinc(II)-S3 complex with NO2- produced a new binuclear Zn(II) complex featuring a coordinated dithiosulfite (S3O2-) along with the formation of perthionitrite (SSNO-), of which the latter subsequently produced nitric oxide (NO) and S42-. The present work, thus, demonstrates the comparative reactivity of a series of binuclear Zn(II)-chalcogenolato/-polychalcogenido complexes for the generation of S2O32-, SeO32-, S3O2-, SSNO-, NO and RSS/RSeS.

Nonheme binuclear transition metal complexes with hydrosulfide and polychalcogenides.

The intriguing chemistry of chalcogen (S, Se)-containing ligands and their capability to bridge multiple metal centres have resulted in a plethora of reports on transition metal complexes featuring hydrosulfide (HS-) and polychalcogenides (En2-, E = S, Se). While a large number of such molecules are strictly organometallic complexes, examples of non-organometallic complexes featuring HS- and En2- with N-/O-donor ligands are relatively rare. The general synthetic procedure for the transition metal-hydrosulfido complexes involves the reaction of the corresponding metal salts with HS-/H2S and this is prone to generate sulfido bridged oligomers in the absence of sterically demanding ligands. On the other hand, the synthetic methods for the preparation of transition metal-polychalcogenido complexes include the reaction of the corresponding metal salts with En2- or the two electron oxidation of low-valent metals with elemental chalcogen, often at an elevated temperature and/or for a long time. Recently, we have developed new synthetic methods for the preparation of two new classes of binuclear transition metal complexes featuring either HS-, or Sn2- and Sen2- ligands. The new method for the synthesis of transition metal-hydrosulfido complexes involved transition metal-mediated hydrolysis of thiolates at room temperature (RT), while the method for the synthesis of transition metal-polychalcogenido complexes involved redox reaction of coordinated thiolates and exogenous elemental chalcogens at RT. An overview of the synthetic aspects, structural properties and intriguing reactivity of these two new classes of transition metal complexes is presented.

Kinetic isotope effect offers selectivity in CO2 reduction.

A binuclear Ni complex with N,O donors catalyzes CO2 reduction via its Ni(I) state. The product distribution when H2O is used as a proton source shows similar yields for CO, HCOOH and H2. However, when D2O is used, the product distribution shows a ∼65% selectivity for HCOOH. In situ FTIR indicates that the reaction involves a Ni-COO* and a Ni-CO intermediate. Differences in H/D KIEs on different protonation pathways determine the selectivity of CO2 reduction.

Reduction of nitrite to nitric oxide and generation of reactive chalcogen species by mononuclear Fe(II) and Zn(II) complexes of thiolate and selenolate.

Comparative reactivity of a series of new Zn(II) and Fe(II) compounds, [(Py2ald)M(ER)] (E = S, R = Ph: M = Zn, 1aZn; M = Fe, 1aFe; E = S, R = 2,6-Me2-C6H3: M = Zn, 1bZn; M = Fe, 1bFe; E = Se, R = Ph: M = Zn, 2Zn; M = Fe, 2Fe), and [(Py2ald)M]22+ (M = Zn, 5Zn; M = Fe, 5Fe) is presented. Compound 1aZn could react with nitrite (NO2-) to produce [(Py2ald)Zn(ONO)] (3Zn), which, upon treatment with thiols and PhSeH (proton source), could regenerate either 1aZn/5Zn and 2Zn respectively, along with the production of nitric oxide (NO) where the yield of NO increases in the order tBuSH ≪ PhCH2SH < PhSH < PhSeH. In contrast to this, 1aFe, 2Fe and 5Fe could affect the direct reduction of NO2- in the absence of protons to generate NO and [{(Py2ald)(ONO)Fe}2-µ2-O] (8Fe). Moreover, 8Fe could regenerate 5Fe and 1aFe/2Fe upon treatment with 4 and 6 equiv. of PhEH (E = S/Se), respectively, along with the generation of NO. Finally, a comparative study of the mononuclear Zn(II) and Fe(II) compounds for the transfer of the coordinated thiolate/selenolate and the generation and transfer of reactive sulfur/selenium species (RES-, E = Se, S) to a series of organic substrates has been provided.

Redox Convergent Synthesis and Reactivity of a Cobalt(III)-Pentasulfido Compound.

A new mononuclear cobalt(III)-pentasulfido compound, [(L)Co(S5 )] (3) has been synthesized by using a convergent redox reaction between elemental sulfur and two new cobalt(II)-thiolato compounds, [(L)Co(SR)] (R=Ph, 2 a; 2,6-Me2 -C6 H4 , 2 b), which in turn were synthesized from a dimeric cobalt(II) complex, [(L)2 Co2 ]2+ (1). Compound 3 features a low-spin, diamagnetic, Co(III) center with a coordinated pentasulfido (S5 2- ) chain and has no precedence in the literature. Compound 3 is highly stable towards reduction with a potential of -1.36 V (vs. Cp2 Fe+ /Cp2 Fe) and gives back 1 upon chemical/electrochemical reduction. Reaction of 3 with phosphines yields back 1 and phosphine sulfides, while protonation of the coordinated S5 2- chain in 3 leads to the formation of 1, elemental sulfur and H2 S. Finally, transfer of the coordinated S5 2- chain in 3 to selected organic compounds, such as MeI, PhCH2 Br and PhCOCl, for the generation of organopolysulfido compounds has been demonstrated.

Cp*Co(III)-Catalyzed C-7 C-C Coupling of Indolines with Aziridines: Merging C-H Activation and Ring Opening.

A Cp*Co(III)-catalyzed directing group-assisted C7 C-C coupling of indolines with aziridines has been developed by merging C-H activation and ring opening. The use of cobalt catalyst, detection of a Co(III) intermediate, and late-stage removal of the directing group are important practical features.