163682-38-0

Basic information

• Product Name: (C₅H₅)2Co⁽¹⁺⁾*Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)^(1-)=[Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)][(C₅H₅)2Co]
• CAS NO: 163682-38-0
• Molecular Weight: 1005.74
• Mol File: 163682-38-0.mol

Chemical Properties

• CAS DataBase Reference: (C₅H₅)2Co⁽¹⁺⁾*Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)^(1-)=[Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)][(C₅H₅)2Co](CAS DataBase Reference)
• NIST Chemistry Reference: (C₅H₅)2Co⁽¹⁺⁾*Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)^(1-)=[Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)][(C₅H₅)2Co](163682-38-0)
• EPA Substance Registry System: (C₅H₅)2Co⁽¹⁺⁾*Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)^(1-)=[Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃)][(C₅H₅)2Co](163682-38-0)

Safety Data

• Hazardous Substances Data: 163682-38-0(Hazardous Substances Data)

Upstream product

• 1277-43-6 cobaltocene 
• 143187-61-5 Re(Br)(CO)3(((C₆H₅)2P)2C₄O₃) 

Relevant articles and documents

Synthesis, redox reactivity, and X-ray diffraction structures of the rhenium carbonyl complexes fac-ReBr(CO)3(bma) and [fac-RBr(CO)3(bma)][Cp2Co]. Structural consequences of electron accession in fac-ReBr(CO)3(bma)

Solvent displacement in the rhenium complex ReBr(CO)3(THF)2 (2) by the redox-active diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) affords the corresponding bma-substituted complex fac-ReBr(CO)3(bma) (3) in near quantitative yield. The same product is also obtained, albeit in lower yield, from BrRe(CO)5 (1) and bma in refluxing 1,2-dichloroethane. fac-ReBr(CO)3(bma) has been isolated and characterized in solution by IR and NMR (31P and 13C) spectroscopies. The oxidation/reduction chemistry of fac-ReBr-(CO)3(bma) was explored by cyclic and rotating disk electrode voltammetric techniques. Two diffusion-controlled one-electron reduction processes at E1/2 = -0.33 V and E1/2 = -1.23 V and an irreversible oxidation at Epa = 1.58 V are observed in CH2Cl2/TBAP at a platinum electrode. The reductive electrochemistry is discussed in the context of a scheme involving the formal reduction of the bma ligand, a property that is common with other known 18 + δ paramagnetic compounds containing an ancillary bma ligand. Reductive bulk electrolyses have been carried out on 3, and the product of one-electron reduction, [fac-ReBr(CO)3(bma)].- (4), has been characterized by IR and UV-vis spectroscopies. Large infrared frequency shifts in the carbonyl stretching bands of the bma ligand in [fac-ReBr(CO)3(bma)].- are observed, as expected for a reduction process confined to the electron-accepting bma ligand. The unequivocal identity of [fac-ReBr(CO)3(bma)].- was independently established by the isolation and structural characterization of the product formed from the cobaltocene reduction of fac-ReBr(CO)3(bma). The molecular structures of compounds 3 and 4 have been determined by single-crystal X-ray diffraction analysis. fac-ReBr(CO)3(bma) crystallizes in the triclinic space group P1: a = 9.855(1) A?, b = 12.1153(4) A?, c = 13.7751(8) A?, α = 85.322(4)°, β = 73.828(6)°, γ = 75.812(6)°, V = 1531.3(2) A?3, Z = 2, dcalc = 1.771 g·cm-3; R = 0.0552, Rw = 0.0771 for 3342 observed reflections. The radical anion [fac-ReBr(CO)3(bma)][Cp2Co], as the CH2Cl2 solvate, crystallizes in the monoclinic space group C2/c: a = 39.600(3) A?, b = 10.2625(2) A?, c = 23.253(2) A?, β = 120.278(7)°, V = 8161(1) A?3, Z = 8, dcalc = 1.793 g·cm-3; R = 0.0511, Rw = 0.0598 for 3811 observed reflections. These two structures permit a direct comparison regarding the consequences of electron accession in fac-ReBr(CO)3(bma). Extended Hu?ckel calculations have been performed on the model compound fac-ReBr(CO)3-(H4bma), the results of which are used to support the electrochemical data and the proposed reduction pathway involving electron addition to the bma ligand.