Oxidative Addition of Diorganyl Ditellurides to [Mn(CO)5]-: Crystal Structures of cis-[Na-18-crown-6-ether.cntdot.2THF][Mn(CO)4(TePh)2], [PPN][(CO)3Mn(.mu.-TePh)3Mn(CO)3], (CO)3Mn(.mu.-TePh)3Co(CO)(.mu.-TePh)2Mn(CO)4, and (CO)4Mn(.mu.-TePh)2Mn(CO)4

[(Te2)3{Mn(CO)3}2{Mn(CO)4}3]– – A Novel Tellurium‐­Manganese Carbonyl with Ufosane‐like Structure

“…For the title compound, altogether seven CO vibrations at 2100m, 2067sh, 2046s, 2037sh, 2004s, 1975s and 1944s cm –1 can be differentiated. This range of vibrations fits well to known compoundswith formal Mn(CO) 3 + and Mn(CO) 4 + fragments (2049–1907 cm –1 ) 26,27. In order to study the thermal stability of [BMIm][(Te 2 ) 3 {Mn(CO) 3 } 2 {Mn(CO) 4 } 3 ], thermogravimetry (TG) was conducted (Figure 5).…”

“…Moreover, [Ph 4 P][Mn 4 (CO) 13 (Te 2 ) 3 ] and [PPn][(TeMe2)Mn(CO)4( μ 5‐Te)( μ 4‐Te)Mn4(CO)12] (PPn:2‐{bis(diisopropylphosphino)‐methyl}‐1‐methylimidazole) – both containing Mn(CO) 3 + and Mn(CO) 4 + fragments – show mean C–O distances in a similar range, as well (114 pm) 17,25. In addition to the C–O distances, the Mn–C distances in [{Te 2 } 3 {Mn(CO) 3 } 2 {Mn(CO) 4 } 3 ] – (178.7(7)–185.8(7) pm) are similar to Mn 2 (CO) 10 , [Ph 4 P][Mn 4 (CO) 13 (Te 2 ) 3 ] or [PPn][(TeMe2)Mn(CO)4( μ 5‐Te)( μ 4‐Te)Mn4(CO)12] (177–184 pm) 17,26…”

An Approach to Heterometallic Complexes with Selenolate and Tellurolate Ligands: Crystal Structures of cis-[Mn(CO)4(SePh)2]-, [(CO)3Mn(μ-SeMe)3Mn(CO)3]-, (CO)4Mn(μ-TePh)2Co(CO)(μ-SePh)3Mn(CO)3, and (CO)3Mn(μ-SePh)3Fe(CO)3

“…Recent work in this laboratory has focused on the syntheses and characterizations of novel metal tellurolate and selenolate complexes via activation of diorganyl dichalcogenides (oxidative addition/nucleophilic displacement) to anionic metallic fragments. Application of anionic metallic fragments for preparation of metal tellurolates/selenolates has been proved to be one of the most versatile routes and to be particularly suitable for d 8 anionic metal carbonyls ([HFe(CO) 4 ] - , [REFe(CO) 4 ] - (E = Se, Te; R = Ph, alkyl), [Mn(CO) 5 ] - , [Re(CO) 5 ] - ). , There have been many reports relevant to the syntheses of metal selenolate and tellurolate complexes. Synthetic approaches, to our knowledge, involve the protolysis including reaction of alkylmetal/metal amido complexes with selenol/tellurol, the metathesis or transmetalation between an alkali-metal selenolate and a metal halide, insertion, nucleophilic cleavage of the E−E (E = Se, Te) bonds by metal hydrides, and the oxidation of metal upon reaction with the diorganyl dichalcogenides. ,, …”

Iron Pyridine-2-thiolate Complexes: Interconversion of [Fe0(CO)4(SC5H4N)]-, cis-[FeII(CO)2(SC5H4N)2], and [FeII(SC5H4N)3]-

“…The anionic SC 5 H 4 N - ligands in cis -[Fe(CO) 2 (SC 5 H 4 N) 2 ] bind to the metal in a bidentate manner, forming four-membered chelate rings (Scheme b,c). The proposed mechanism, shown in Scheme b,c, involves oxidative addition of bis(2-pyridyl) disulfide to the anionic [Fe(CO) 4 (SC 5 H 4 N)] - , 5b,c,7a-c possibly via the intermediate fac -[Fe II (CO) 3 (SC 5 H 4 N) 3 ] - . (In a similar fashion, the reaction of [HFe(CO) 4 ] - with 2 equiv of (S(C 4 H 3 S)) 2 in THF at ambient temperature leads to a thermally stable crystalline solid fac -[Fe II (CO) 3 (SC 4 H 3 S) 3 ] - characterized by X-ray crystallography 7d…”

“…We previously reported investigations into the biomimetic nickel-site structures of [NiFeSe] hydrogenase (nickel is ligated to one Se atom, one to two S/Cl atoms, and three to four N/O atoms) 4 and CO dehydrogenase 5a and the oxidative addition of RE−ER (E = Te, Se; R = Ph, alkyl) to anionic metal carbonyl fragments. 5b-e In this work, we report a study of the interconversion of the pyridine-2-thiolate complexes [Fe 0 (CO) 4 (SC 5 H 4 N)] - , cis -[Fe II (CO) 2 (SC 5 H 4 N) 2 ], and [Fe II (SC 5 H 4 N) 3 ] - (Scheme ).

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