Photolytisch induzierte Reaktionen von CpCo(CO)₂(Cp = C₅H₅, C₅H₄Me, C₅Me₅ und C₅Ph₅) mit Thiiran zu dinuklearen 1,2-Ethandithiolato-S-S-Komplexen / Photolytically Induced Reactions of CpCo(CO)₂ (Cp = C₅H₅, C₅H₄Me, C₅Me₅ and C₅Ph₅) with Thiirane Yielding Dinuclear 1,2-Ethanedithiolato-S,S Complexes

Abstract

The complexes CpCo(CO) 2 (Cp = C 5 H 5 , C 5 H 4 Me, C 5 Me 5 and C 5 Ph 5 ) (1a -d) react with thiirane C 2 H 4 S under UV-irridiation in THF to form the dinuclear µ 2 -1,2-ethanedithiolate-S,S complexes [(CpCo) 2 (µ 2 -S 2 C 2 H 4 )] (2a -d) as main products. Using column chromatography, in case of Cp = C 5 H 5 Me also the dimeric complex [C 5 H 4 MeCo(µ 2 -S 2 C 2 H 4 )] 2 (3b), in case of Cp = C 5 Ph 5 the mixed disulfido-sulfido complex [(C 5 Ph 5 Co) 2 (µ 2 -S 2 )(µ 2 -S)] (4d) were isolated in small yields. Only 2a reversibly adds SO 2 gas to form the µ 2 -SO 2 complex [(C 5 H 5 CoSCH 2 ) 2 (µ 2 -SO 2 )] (5a). A bromo ligand bridging the Co atoms can be introduced by the reaction of [(C 5 Me 5 CoBr 2 )] 2 (6c) with 1,2-ethanedithiol which gives the cationic complex [(C 5 Me 5 CoSCH 2 ) 2 (µ 2 -Br)] 2 CoBr 4 (7c). All compounds have been characterized by their IR, 1 H and 13 C NMR and MS spectra and compounds 2b -d, 3b and 7c by X-ray structure analyses, which prove the pseudo tetrahedral skeleton (CpCoS) 2 and the ethane bridge between both sulfur atoms. 3b shows, however, a new unsymmetrical bonding mode of both dithiolato bridges with η 1 -S und µ 2 -S ligand functions.

The Chemistry of Transition Metals with Three-Membered Ring Heterocycles

“…Attempts by the authors to independently prepare the complex 349 also led to the evolution of ethylene. The generation of bismetallic bridged sulfido and ethylene dithiol complexes with thiiranes has also been observed by the Lorenz group with CpCo­(CO) 2 …”

(η4-Tetraphenylcyclobutadiene)-(η5-pentaphenylcyclopentadienyl)-cobalt

“…The distances between the cyclopentadienyl carbon and the phenyl ipso carbons are longer than the corresponding distances at the cy tadiene ring (average distance, 1.484(4) vs. 1.469(4) Å ). Whereas all phenyl rings a out of the planes of the co-ordinated rings away from the Co atom, this effect is st in the cyclobutadiene ring (average bending angle [2,4] [23], NICDIM [24], POHXAL [25], REXNEO [26], TUPQAW [27]), an contain a [Co(C4Ph4)(C5R5)] (R ≠ H) core (MEYQAI, MEYQOW [28], NEVDAT [29 UQUE [22]). Although many structures have two C5Ph5 rings (including [Co(C5 POHXAL), none has exclusively two C4Ph4 rings.…”

“…We decided to use the mentioned C5Ph5 structures (except for REX which is a binuclear compound) and the C4Ph4 structures NEVDAT, UZUQUE, MUL10 and [Co(C5H5)(C4Ph4)] (CPBUCO01, [30] for comparison with compound relevant data are presented in Table 1. ] core (GAHRUC [23], NICDIM [24], POHXAL [25], REXNEO [26], TUPQAW [27]), and four contain a [Co(C 4 Ph 4 )(C 5 R 5 )] (R = H) core (MEYQAI, MEYQOW [28], NEVDAT [29], UZUQUE [22]). Although many structures have two C 5 Ph 5 rings (including [Co(C 5 Ph 5 ) 2 ] + , POHXAL), none has exclusively two C 4 Ph 4 rings.…”

Progress toward the Isolation of Late Metal Terminal Sulfides

“…[78] Finally, photolysis of [Cp*Co(CO) 2 ] (23) in the presence of ethylene sulfide results in formation of [Cp*Co] 2 (μ:η 2 :η 2 -SCH 2 CH 2 S) (25), which was proposed to form via the terminal Co sulfide, [Cp*Co(S)] (24) (Scheme 7). [79] A plausible mechanism of formation involves attack of ethylene sulfide by 24 to form the ethylene disulfide fragment, [Cp*Co(SCH 2 CH 2 S)], followed by coupling to another equivalent of 23. Importantly, this reaction highlights the nucleophilicity of the sulfide ligand in 24, which is also mirrored by the reactivity of our Ni II sulfide (see section 3.3).…”