1208128-70-4

Upstream product

• 109-69-3 n-Butyl chloride 
• 6781-98-2 2,6-dimethyl-1-chlorobenzene 
• 623-12-1 4-chloromethoxybenzene 
• 98-56-6 4-chlorobenzotrifluoride 
• 1126-46-1 Methyl 4-chlorobenzoate 
• 352-33-0 1-Chloro-4-fluorobenzene 
• 106-43-4 para-chlorotoluene 
• 108-90-7 chlorobenzene 
• 100-44-7 benzyl chloride 
• 106-46-7 para-dichlorobenzene 
• 7051-16-3 1-chloro-3,5-dimethoxybenzene 
• 2402-78-0 2,6-dichloropyridine 
• 99-91-2 para-chloroacetophenone 
• 844642-16-6 [(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)Co(CH₂SiMe₃)] 

Downstream Products

• 1379381-26-6 [Co(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)(CH₂CMe₂Ph)] 
• 436857-75-9 dichloro(2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine)cobalt(II) 
• 1379381-27-7 [Co(2,6-bis(2,6-dimethylphenyliminoethyl)pyridine)(η3-allyl)] 

Relevant academic research and scientific papers

Radical mechanisms in the reaction of organic halides with diiminepyridine cobalt complexes

The formally Co(0) complex LCo(N2) (L = 2,6-bis(2,6- dimethylphenyliminoethyl)pyridine) can be prepared via either Na/Hg reduction of LCoCl2 or hydrogenolysis of LCoCH2SiMe3. In the latter reaction, LCoH could be trapped by reaction with N≡CC 6H4-4-Cl to give LCoN=CHC6H4-4-Cl. LCo(N2) reacts with many alkyl and aryl halides RX, including aryl chlorides, to give a mixture of LCoR and LCoX in a halogen atom abstraction mechanism. Intermediacy of free alkyl and aryl radicals is confirmed by the ring-opening of cyclopropylmethyl to crotyl, and the rearrangement of 2,4,6-tBu3C6H2 to 3,5- tBu2C6H3CMe2CH 2, before binding to Co. The organocobalt species generated in this way react further with activated halides R′X (alkyl iodides; allyl and benzyl halides) to give cross-coupling products RR′ in what is most likely again a halogen abstraction mechanism. DFT studies support the proposed radical pathways for both steps. MeI couples smoothly with LCoCH2SiMe 3 to give LCoI and CH3CH2SiMe3, but the analogous reaction of tBuI leads in part to radical attack at the 3 and 4 positions of the pyridine ring to form (tBu 2-L)CoI and (tBu2-L)CoI2.

Binuclear oxidative addition of aryl halides

Reaction of LCoCH2SiMe3 (L = 2,6-bis[2,6- dimethylphenyliminoethyl]pyridine) with H2 produces LCo(N 2), presumably via intermediate LCoH. Reaction of LCo(N2) (prepared in this way or via reaction of LCoCl2 with Na/Hg) with aryl halides ArX (X = Cl, Br, I) produces LCoAr and LCoX in a ratio depending on the nature of Ar and X. For X = Cl, the reaction is slowest but also produces the largest amount of LCoAr. Electron-withdrawing substituents both accelerate the reaction and improve the yield of LCoAr. Computational studies support a radical mechanism for this reaction, involving displacement of N2 to give LCo(XAr) followed by loss of the Ar radical, which then binds to a second Co(0) moiety.