Wen-Feng Liaw

SS Bond-activation of diorganyl disulfide by anionic [Mn(CO)5]−: crystal structures of [MnII(SC5H4NO)3]− and [(CO)3Mn(μ-SR)3Co(μ-SR)3Mn(CO)3]− (R=C6H4NHCOPh)

Abstract The SS bond-activation of diorganyl disulfide by the anionic metal carbonyl fragment [Mn(CO) 5 ] − gives rise to an extensive chemistry. Oxidative decarbonylation addition of 2,2′-dithiobis(pyridine- N -oxide) to [Mn(CO) 5 ] − , followed by chelation and metal-center oxidation, led to the formation of [Mn II (SC 5 H 4 NO) 3 ] − ( 1 ). The effective magnetic moment in solid state by SQUID magnetometer was 5.88 μ B for complex 1 , which is consistent with the Mn II having a high-spin d 5 electronic configuration in an octahedral ligand field. The average Mn(II)S, SC and NO bond lengths of 2.581(1), 1.692(4) and 1.326(4) A, respectively, indicate that the negative charge of the bidentate 1-oxo-2-thiopyridinato [SC 5 H 4 NO] − ligand in complex 1 is mainly localized on the oxygen atom. The results are consistent with thiolate-donor [SC 5 H 4 NO] − stabilization of the lower oxidation state of manganese (Mn(I)), while the O , S -chelating [SC 5 H 4 NO] − ligand enhances the stability of manganese in the higher oxidation state (Mn(II)). Activation of SS bond as well as OH bond of 2,2′-dithiosalicylic acid by [Mn(CO) 5 ] − yielded [(CO) 3 Mn(μ-SC 6 H 4 C(O)O) 2 Mn(CO) 3 ] 2− ( 4 ). Oxidative addition of bis( o -benzamidophenyl) disulfide to [Mn(CO) 5 ] − resulted in the formation of cis -[Mn(CO) 4 (SR) 2 ] − (R=C 6 H 4 NHCOPh) which was employed as a chelating metallo ligand to synthesize heterotrinuclear [(CO) 3 Mn(μ-SR) 3 Co(μ-SR) 3 Mn(CO) 3 ] − ( 8 ) possessing a homoleptic hexathiolatocobalt(III) core.

Synthesis and reactivity of fac-[Fe(CO)3(SR)3]− (R=C7H4SN, C4H3S, C4H2O-o-CH3) and heterotrimetallic Fe(II)–Ni(II)–Fe(II)–thiolate complex

Abstract The reaction of 2 equiv. of diorganyl disulfides, (bis(2-benzothiazolyl) disulfide, di(2-thienyl) disulfide, and bis(2-methyl-3-furyl) disulfide), with 1 equiv. of [HFe(CO) 4 ] − affords the stable, tridentate fac -[Fe(CO) 3 (SR) 3 ] − (R=C 7 H 4 SN ( 1 ); C 4 H 3 S ( 2 ); C 4 H 2 O- o -CH 3 ( 3 )) via the formation of intermediate [RSFe(CO) 4 ] − , respectively. In contrast, oxidative addition of 2-aminophenyl disulfide to [Fe(CO) 4 (SC 6 H 4 - o -NH 2 )] − , obtained from reaction of [HFe(CO) 4 ] − and 2-aminophenyl disulfide, and concomitant displacement of [SC 6 H 4 - o -NH 2 ] − leads to the neutral monomeric compound cis -[Fe(CO) 2 (SC 6 H 4 - o -NH 2 ) 2 ] ( 6 ). Obviously, the reactivity and stability of the iron–thiolate derivatives may be tailored by pendant ligand selection, and the reaction pathway is tailored according to the bond strength inherent in the organodisulfides and to the nucleophilicity of thiolate atoms in [RSFe(CO) 4 ] − complexes. In particular, compounds fac -[Fe(CO) 3 (SR) 3 ] − serve as chelating metalloligand and intermetal thiolate ligand-transfer reagent to synthesize the linear heterotrinuclear [(CO) 3 Fe(μ-SR) 3 Ni(μ-SR) 3 Fe(CO) 3 ] ( 4 ) (R=C 4 H 2 O- o -CH 3 ) and the neutral [Fe(CO) 2 (SC 4 H 3 S) 2 (bipy)] ( 5 ) (bipy=bipyridine).

Dalton communications. Crystal structure of [Na·3thf][Fe(CO)3(SePh)3] and [N(PPh3)2][Fe(CO)3(SePh)3]·0.5thf (thf = tetrahydrofuran): evidence for Na+⋯ sePh and long-range Na+⋯ FeII interactions

The reaction between Na[HFe(CO)4] and (PhSe)2 Yielded Na[Fe(CO)3(SePh)3] which crystallized as [Na·3thf][Fe(CO)3(SePh)3] in which three tetrahydrofuran (thf) molecules and the [Fe(CO)3(SePh)3]– anion surround the sodium cation; in the corresponding crystal structure of [N(PPh3)2][Fe(CO)3-(SePh)3]·0.5thf the cations and anions are discrete entities.

Chelating and ligand-transfer studies of the complexes cis-[Mn(CO)4(SeR)2]−: crystal structures of heterotrinuclear [(CO)4Mn(μ-SeMe)2Ni(μ-SeMe)2Mn(CO)4] with a distorted square planar NiII–selenolate core and [PPN]2[Cl2Pd(μ-SePh)2PdCl2]

Abstract Trinuclear selenolate complexes [(CO) 4 Mn(μ-SeR) 2 Ni(μ-SeR) 2 Mn(CO) 4 ] (R=Me, Ph) containing a distorted square planar Ni(Se) 4 core have been synthesized by the reaction of Ni(NO 3 ) 2  · 6H 2 O/NiCl 2 with the chelating metalloligand cis -[PPN][Mn(CO) 4 (SeR) 2 ] in MeCN. Their structures were elucidated on the basis of IR, UV–Vis, CV, and NMR spectra. X-ray crystallography confirmed the heterotrinuclear structure in the solid state with a Ni II –Se distance of 2.331(1) A, and a Ni II ⋯Mn I distance of 3.428(2) A (average). The dependence of geometry on electron population and the larger Ni II ⋯Mn I distances are adopted to rationalize the construction of the complex [(CO) 4 Mn(μ-SeMe) 2 Ni(μ-SeMe) 2 Mn(CO) 4 ] with a distorted square planar Ni II (Se) 4 core. Further reaction of cis -[PPN][Mn(CO) 4 (SePh) 2 ] with PdCl 2 afforded [PPN] 2 [Cl 2 Pd(μ-SePh) 2 PdCl 2 ]. Its structure has been determined. This investigation shows that cis -[Mn(CO) 4 (SeR) 2 ] − serves as a chelating metalloligand and selenolate ligand-transfer reagent.

Heterotrinuclear complexes containing a hexaselenolato-zinc(II), -cadmium(II), -nickel(II) or -iron(II) core: crystal structures of [(OC)3Fe(µ-SePh)3M(µ-SePh)3Fe(CO)3] (M = Zn, Cd, Ni or Fe) and [Fe(CO)2(phen)(SePh)2] (phen = 1,10-phenanthroline)

A series of linear trinuclear selenolate complexes of the general type [(OC)3Fe(µ-SePh)3M(µ-SePh)3Fe(CO)3] (M = ZnII 1, CdII 2, NiII 3 or FeII 4) has been synthesized by reaction of the appropriate [M(H2O)n]2+ with the chelating metalloligand fac-[N(PPh3)2][Fe(CO)3(SePh)3] in acetonitrile. Their structures were elucidated on the basis of IR, UV/VIS, NMR spectra and X-ray crystallography. Compounds 1–4 are structurally related, each containing two tridentate metalloligands resulting in a MSe6 co-ordination environment of virtual Oh symmetry. Further reaction of 4 with 3 equivalents of 1,10-phenanthroline (phen) initially afforded the intermediate [Fe(phen)3][Fe(CO)3(SePh)3]2 but eventually neutral [Fe(CO)2(phen)(SePh)2] 5 was formed as the sole product. Its crystal structure has been determined. This investigation shows that fac-[Fe(CO)3(SePh)3]– serves as a tridentate chelating metalloligand and selenolate ligand-transfer reagent.