313706-01-3

Upstream product

• 603-35-0 triphenylphosphine 
• 101-02-0 triphenyl phosphite 
• 1159-54-2 tri(4-chlorophenyl)phosphine 
• 75-09-2 dichloromethane 
• 1038-95-5 Tri(p-tolyl)phosphine 

Downstream Products

• 897661-32-4 (C₅H₄NH₂)Co(S₂C₂(COOCH₃)H) 
• 897661-33-5 (C₅H₄NH(p-SO₂C₆H₄Me))Co(S₂C₂H₂) 
• 897661-34-6 (C₅H₄NH(p-SO₂C₆H₄Me))Co(S₂C₂(COOMe)H) 

Relevant academic research and scientific papers

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).

Novel phosphine- and phosphite-induced imido migration to a cyclopentadienyl ring in an imido-bridged cobaltadithiolene complex

The mechanism of phosphine- and phosphite-induced migration of the imido group from sulfur to a Cp ring in a tosylimido-bridged cobaltadithiolene complex was investigated, and a probable intermediate was isolated and characterized. The presence of a large excess of PPh3 causes the formation of the imido- and phosphine-substituted Cp complex.

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.