47854-84-2

Upstream product

• 53433-12-8 [bis(triphenylphospine)nitrogen⁽¹⁺⁾][Co(CO)4] 
• 56-34-8 tetraethylammonium chloride 
• 3017-60-5 cobalt(II) thiocyanate 
• 22560-16-3 lithium triethylborohydride 
• 603-35-0 triphenylphosphine 
• 15226-74-1 dicobalt octacarbonyl 

Downstream Products

• 10170-27-1 Co₂(CO)6(PPh₃)2 
• 14911-28-5 Co₂(CO)6{P(C₄H₉-n)3}2 
• 118400-48-9 Co₂(CO)6(P(C₆H₅)3)(P(C₄H₉)3) 

Relevant academic research and scientific papers

Synthesis, structure and possible formation pathway of a novel cobalt carbonyl compound with new type B-O bond, Co(CO)3 (PPh3)2BEt3, and mixed metal Co-Fe-S cluster with possible nonlinear optical property, [Et4N][CoFe2 (CO)8S(PPh3)]

Reaction of Co(CNS)2 with Fe2S2(CO)6, LiBEt3H and PPh3 in THF-MeCN resulting in a novel cobalt carbonyl complex, Co(CO)3(PPh3)2BEt3 (1) and mixed-metal Co-Fe-S cluster compound, [Et4N]Fe2Co(CO)8S(PPh3)] (2). The structures of 1 and 2 were determined from X-ray three dimension data. Structure studies reveal that 1 is a new cobalt carbonyl complex containing a novel B-O bond of 1.601(5) ? in which the oxygen atom is from metal carbonyl and the B atom is from BEt3 and 2 contained a triangular pyramid mixed-metal Co-Fe-S core [CoFe2S]- with Co-S of 2.189, Fe-S of 2.208, Co-Fe of 2.56 and Fe-Fe of 2.58 ?. Theoretical calculation on 1 and 2 shows that B-O bonding energy of complex 1 is lower than that of normal covalent bonding and 2 possesses a calculated nonlinear optical first molecular hyperpolarizability component of 28.5 × 10-30 esu. The possible formation pathway of 1 and 2 was discussed.

Oxidation-reduction of carbonylcobalt cation-anion pairs in coupling to dimeric cobalt carbonyls

The carbonylcobalt cation Co(CO)3(PPh3)2+ reacts with the anionic Co(CO)3PPh3- upon mixing to afford quantitative yields of the dimeric Co2(CO)6(PPh3)2. The same coupling occurs with the analogous Bu3P-substituted cation-anion pair to produce Co2(CO)6(PBu3)2, but at a significantly attenuated rate. Cross couplings of the substitution-inert Co(CO)3P2+ and Co(CO)3P′-, as well as the reverse phosphine combination, afford mixtures of Co2(CO)6P2, Co2(CO)6PP′ and Co2(CO)6P′2 diagnostic of extensive ligand (P,P′) scramblings. Facile ligand exchange of reactive intermediates is also indicated by the production of only Co2-(CO)6(PBu3)2 from Co(CO)3(PPh3)2+ and Co(CO)3PPh3- when carried out in the presence of added PBu3-without materially affecting the coupling rate. The marked solvent and salt effects together with the observation of characteristic charge-transfer absorption bands point to the contact ion pairs [Co(CO)3P2+] [Co(CO)3P′-] as critically involved in the rate-limiting activation process. A general mechanistic formulation is presented in Scheme II, in which the contact ion pair evolves into the radical pair consisting of the 19-electron Co(CO)3P2? and the 17-electroh Co(CO)3P′?. The behavior of these carbonylcobalt radicals is independently established in the preparative and transient electrochemistry of their precursors Co(CO)3P2+ and Co(CO)3P′- in reduction (Ec) and oxidation (Ea), respectively. Indeed the reactivity patterns in ion-pair, annihilation parallel the differences in the redox potentials J(Ec - Ea) as a direct measure of the driving force for electron transfer. Cyclic voltammetry is shown to be a particularly useful probe to demonstrate (i) the rapid dimerization rates of the 17-electron radicals to afford dicobalt carbonyls and (ii) the facile exchange of phosphine ligands between Co(CO)3P? and Co(CO)3P′? via the highly labile 19-electron intermediates Co(CO)3PP′?. Although the electron-transfer mechanism in Scheme II accounts for all the experimental observations relating to ion-pair annihilation, the possibility of alternative nonradical pathways previously proposed is also discussed.