Richard S. Henderson

The dithiobis(tricarbonyliron) dianion: Improved preparation and new chemistry

Abstract The reaction of two molar equivalents of lithium triethylborohydride in THF −78° with one of (μ-S2Fe2(CO6) results in formation of the [S2Fe2(CO)6]2− dianion in essentially quantitative yield. Reactions of this dianion with organic halides and with halides of tin, germanium, silicon and nickel are reported. Protonation of the dianion produces (μ-HS)2Fe2(CO)6.

Seleniumselenium bond reactions of μ-(diselenium)bis(tricarbonyliron), an inorganic mimic of organic diselenides

Abstract μ-(Diselenium)bis(tricarbonyliron), (μ-Se2)Fe2(CO)6, has been found to have reactivity typical of organic diselenides, RSeSeR. Reaction with two molar equivalents of LiBEt3H converts (μ-Se2)Fe2(CO)6 to the dianion, (μ-LiSe)2Fe2(CO)6. Organolithium reagents, RLi, cleave its SeSe bond, giving (μ-LiSe)(μ-RSe)Fe2(CO)6. Low valent transition metal species, e.g., (Ph3P)2Pt, insert into the SeSe bond. (μ-Se2)Fe2(CO)6 is fragmented by the action of dicobalt octacarbonyl, giving (μ3-Se)FeCo2(CO)9.

Chemistry of μ-dithiobis(tricarbonyliron), an inorganic mimic of organic disulfides: II. Nucleophilic SS bond cleavage by organolithium and organomagnesium reagents☆

Abstract Organolithium and Grignard reagents cleave the SS bond of (μ-S 2 Fe 2 CO 6 at −78°C to give intermediates of type (μ-RS)(μ-MS)Fe 2 (CO) 6 , (M = Li or MgX). These may be alkylated with organic halides to produce complexes of type (μ-RS)(μ-R′S)Fe 2 (CO) 6 and protonated to yield (μ-RS)(μ-HS)Fe 2 (CO) 6 .

Di-μ-thiolbis(tricarbonyliron),(μ-HS)2 Fe2(CO)6: an inorganic mimic of organic thiols

Abstract Di-μ-thiolbis(tricarbonyliron) reacts at room temperature with organic halides in the presence of triethylamine to give high yields of products in wh

Reactions of lithium bis(μ-phenylphosphido)-bis(tricarbonyliron), (μ-PhPLi)2Fe2(CO)6, with organic halides. A novel anionic rearrangement of a chelating diphosphido ligand

Abstract Reactions of (μ-PhPLi) 2 Fe 2 (CO) 6 with various organic mono- and di-halides resulted in alkylation of the phosphorus atoms. The use of α,ω-dihalides gave products with an organic bridge between the two phosphorus atoms. Deprotonation of the complex where the organic bridge is an o-xylylene group at 20°C gives an anion ( 16 ) which undergoes a novel rearrangement via intramolecular attack at an iron atom to produce 19 .

(μ-dithio)bis(tricarbonyliron) as an organic disulfide mimic: insertion of low-valent metal species into the sulfursulfur bond

Abstract Low valent metal species: (Ph 2 PCH 2 CH 2 PPh 2 )Ni 0 , (Ph 3 P) 2 Pd 0 , (Ph 3 P) 2 Pt 0 , η 5 -C 5 H 5 Co I and (CH 3 ) 2 Sn II insert into the SS bond of (μ-S 2 )Fe 2 (CO) 6 under mild conditions. Identical products were obtained by reactions of the dianion, [(μ-S 2 )Fe 2 (CO) 6 ] 2− with the corresponding metal chlorides.

The Reaction of μ-dithiobis(tricarbonyliron) with dimanganese decacarbonyl: a novel product and an interesting structural problem

Abstract The photo-induced reaction of (μ-S2)Fe2(CO)6 and Mn2(CO)10 in tetrahydrofuran solution gave a complex of composition S2Fe2Mn2(CO)14. A combination of X-ray crystallography, Mossbauer spectroscopy, mass spectroscopy and elemental analysis established this composition and the structure as Fe2Mn(CO)9(μ3-S)(μ4-S)Mn(CO)5, the Fe2Mn system of which contains one FeFe and one FeMn bond.

Photochemically induced insertion of acetylenes into μ-dithiobis(tricarbonyliron)

Abstract Hexafluoro-2-butyne and the dimethyl and diethyl esters of acetylenedicarboxylic acid insert into the sulfursulfur bond of μ-dithiobis(tricarbonyliron) upon UV irradiation to give dithiolene complexes of type IV.

Phosphaacetylenehexacarbonyldicobalt complexes: new cluster lewis bases

Abstract The reaction of RCCl 2 PCl 2 (R = CH 3 , C 6 H 5 , (CH 3 ) 3 Si) with dicobalt octacarbonyl in THF at −78°C gave the new (RCP)Co 2 (CO) 5 complexes, which contain the CPCo 2 cluster unit, as air-sensitive red oils. The complex with R = CH 3 reacted with (OC) 5 M-THF to give the corresponding M(CO) 5 (M = Cr, W) adducts and the complex with R = C 6 H 5 could be acetylated in the para position with CH 3 C(O)Cl/AlCl 3 .