86543-67-1

Basic information

• Product Name: (η(5)-cyclopentadienyl)[1,2-bis(methoxycarbonyl)ethenethiolato-κS]cobalt(III)
• Synonyms: (η(5)-cyclopentadienyl)[1,2-bis(methoxycarbonyl)ethenethiolato-κS]cobalt(III)
• CAS NO: 86543-67-1
• Molecular Weight: 330.331
• Mol File: 86543-67-1.mol
• Article Data: 5

Chemical Properties

• CAS DataBase Reference: (η(5)-cyclopentadienyl)[1,2-bis(methoxycarbonyl)ethenethiolato-κS]cobalt(III)(CAS DataBase Reference)
• NIST Chemistry Reference: (η(5)-cyclopentadienyl)[1,2-bis(methoxycarbonyl)ethenethiolato-κS]cobalt(III)(86543-67-1)
• EPA Substance Registry System: (η(5)-cyclopentadienyl)[1,2-bis(methoxycarbonyl)ethenethiolato-κS]cobalt(III)(86543-67-1)

Safety Data

• Hazardous Substances Data: 86543-67-1(Hazardous Substances Data)

Upstream product

• 762-42-5 dimethyl acetylenedicarboxylate 
• 121-45-9 phosphorous acid trimethyl ester 
• 75-09-2 dichloromethane 
• 603-35-0 triphenylphosphine 
• 1038-95-5 Tri(p-tolyl)phosphine 
• 1159-54-2 tri(4-chlorophenyl)phosphine 
• 101-02-0 triphenyl phosphite 
• 86543-64-8 (η-cyclopentadienyl)(1,2-diphenyl-1,2-ethylenedithiolato)cobalt(III) 

Downstream Products

• 620178-78-1 [(cyclopentadienyl)Co((NH)S(C₆H₂FNO₂))] 

Relevant articles and documents

Imido-transfer reactions to carbonyl moiety induced by the reactions of imido-bridged cobaltadithiolene complexes with trivalent phosphorus halides

The reactions of the imido-bridged cobaltadithiolene complexes [CpCo{S2C2(COOMe)2}(NR)] (R=Ts, Ms) with PCl3 led to the imido-transfer reactions to the carbonyl moiety, and these reactions gave the novel imine c

Electrochemistry and Reactivity of Cobaltadithiolene Complexes Having Sulfilimine Structures: Effect of Phosphorus Ligand Basicity and Cone Angle on the Electrochemical Behavior and on the Imido Migration to the Cp Ring

Various types of cobaltadithiolene complexes having the sulfilimine structure CpCo[S(NTs)SC2(COOMe)2](PR3) were newly synthesized. The lifetimes of the sulfilimine complexes are influenced by the basicities and by the cone angles of PR3 ligands used. Some of the sulfilimine complexes rapidly eliminate PR3 ligands by a one-electron reduction (PR3 = PPh3, P(OPh)3, P(p-C6H4Me)3, P(p-C6H 4Cl)3, PCy3, P(p-C6H 4OMe)3) to give the precursor of the sulfilimine complex, the imido-bridged cobaltadithiolene adduct [CpCo{S2C 2(COOMe)2}(NTs)]. On the other hand, the complexes of PBu3 and P(OMe)3 were stable during a one-electron reduction. The elimination of the imido group (NTs) by a second reduction was confirmed in all of the sulfilimine complexes. The investigation of the reactivity of the sulfilimine complexes showed that some of the sulfilimine complexes were the intermediates in the imido migration to the Cp ring (PR 3 = PPh3, P(OPh)3, P(p-C6H 4Me)3, P(p-C6H4Cl)3). The basicities (or nucleophilicities) of PR3 were important parameters for the imido migration. Sulfilimine complexes containing strongly nucleophilic PR3 ligands (PR3 = P(p-C6H 4OMe)3, PBu3, P(OMe)3) did not undergo migration of the imido group. In the formation of the disubstituted Cp complex [{C5H3(NTs)(PR3)}Co{S2C 2(COOMe)2}], the basicity (or nucleophilicity) of PR 3 ligands is also an important parameter (PR3 = PPh 3, P(p-C6H4Me)3).

Formation and reaction of three-membered cobaltathiaziridine ring in (η5-cyclopentadienyl)(substituted imido-κN-thio-κS-ethene-2-thiolato-κS)cobalt(III). Ring opening and closure and transfer of imido group

Three-membered cobaltathiaziridine rings are formed in the reactions of [CpCo{S2C2(COOMe)2)2}] either with some azides (RN3: p-toluenesulfonyl azide (TsN3), methanesulfonyl azide (MsN3), and ethyl azidoformate (EtOOCN3)) or with N-(phenyliodonio)-p-toluenesulfonamidate (PhI = NTs) to afford imido-bridged complexes, [CpCo{S2C2(COOMe)2}(NR)]. The ring undergoes unique ring opening and reforming reactions. Hydrogen chloride brings about the cleavage of the Co-N bond to give S-iminodithiolatocobalt(III) complexes [Cp(Cl)Co{S(NR)-C(COOMe)-C(COOMe)-S)}], which very easily regenerates the cobaltathiaziridine ring on treatment with bases, such as pyridine and even with the very weak base, water. The reaction with triphenylphosphine at room temperature results in the ring opening to give an ylide. The heating of a benzene solution of the ylide at 80°C (under reflux) gives a product in which a sulfonylimido moiety migrates to a carbon atom of the cyclopentadienyl ring. The reduction halfwave potential values of the imido-bridged complexes depend on the substituent of bridging moiety. The CV of sulfonylimido-bridged complex shows one-electron two-step reduction processes. We found that the reductant of the original complex is regenerated not by the first reduction, but by the second reduction according to CV and OTTLE measurements.