Synthesis and characterization of reduced heme and heme/copper carbonmonoxy species

Carbon monoxide readily binds to heme and copper proteins, acting as a competitive inhibitor of dioxygen. As such, CO serves as a probe of protein metal active sites. In our ongoing efforts to mimic the active site of cytochrome c oxidase, reactivity toward carbon monoxide offers a unique opportunity to gain insight into the binding and spectroscopic characteristics of synthetic model compounds. In this paper, we report the synthesis and characterization of CO-adducts of ((5/6)L)Fe(II), [((5/6)L)Fe(II)...Cu(I)](B(C(6)F(5))(4)), and [(TMPA)Cu(I)(CH(3)CN)](B(C(6)F(5))(4)), where TMPA = tris(2-pyridylmethyl)amine and (5/6)L = a tetraarylporphyrinate tethered in either the 5-position ((5)L) or 6-position ((6)L) to a TMPA copper binding moiety. Reaction of ((5/6)L)Fe(II) [in THF (293 K): UV-vis 424 (Soret), 543-544 nm; (1)H NMR delta(pyrrole) 52-59 ppm (4 peaks); (2)H NMR (from ((5)L-d(8))Fe(II)) delta(pyrrole) 53.3, 54.5, 55.8, 56.4 ppm] with CO in solution at RT yielded ((5/6)L)Fe(II)-CO [in THF (293 K): UV-vis 413-414 (Soret), 532-533 nm; IR nu(CO)(Fe) 1976-1978 cm(-1); (1)H NMR delta(pyrrole) 8.8 ppm; (2)H NMR (from ((5)L-d(8))Fe(II)-CO) delta(pyrrole) 8.9 ppm; (13)C NMR delta((CO)Fe) 206.8-207.1 ppm (2 peaks)]. Experiments repeated in acetonitrile, acetone, toluene, and dichloromethane showed similar spectroscopic data. Binding of CO resulted in a change from five-coordinate, high-spin Fe(II) to six-coordinate, low-spin Fe(II), as evidenced by the upfield shift of the pyrrole resonances to the diamagnetic region ((1)H and (2)H NMR spectra). Addition of CO to [((5/6)L)Fe(II)...Cu(I)](B(C(6)F(5))(4)) [in THF (293 K): UV-vis ((6)L only) 424 (Soret), 546 nm; (1)H NMR delta(pyrrole) 54-59 ppm (multiple peaks); (2)H NMR (from [((5)L-d(8))Fe(II).Cu(I)](B(C(6)F(5))(4))) delta(pyrrole) 53.4 ppm (br)] gave the bis-carbonyl adduct [((5/6)L)Fe(II)-CO...Cu(I)-CO](B(C(6)F(5))(4)) [in THF (293 K): UV-vis ((6)L only) 413 (Soret), 532 nm; IR nu(CO)(Fe) 1971-1973 cm(-1), nu(CO)(Cu) 2091-2093 cm(-1), approximately 2070(sh) cm(-1); (1)H NMR delta(pyrrole) 8.7-8.9 ppm; (2)H NMR (from [((5)L-d(8))Fe(II)-CO...Cu(I)-CO](B(C(6)F(5))(4))) delta(pyrrole) 8.9 ppm; (13)C NMR delta((CO)Fe) 206.8-208.1 ppm (2 peaks), delta((CO)Cu) 172.4 ((5)L), 178.2 ((6)L) ppm]. Experiments in acetonitrile, acetone, and toluene exhibited spectral features similar to those reported. The [((5/6)L)Fe(II)-CO.Cu(I)-CO](B(C(6)F(5))(4)) compounds yielded (CO)(Fe) spectra analogous to those seen for ((5/6)L)Fe(II)-CO and (CO)(Cu) spectra similar to those seen for [(TMPA)Cu(I)-CO](B(C(6)F(5))(4)) [in THF (293 K): IR nu(CO)(Cu) 2091 cm(-1), approximately 2070(sh) cm(-1); (13)C NMR delta((CO)Cu) 180.3 ppm]. Additional IR studies were performed in which the [((5)L)Fe(II)-CO...Cu(I)-CO](B(C(6)F(5))(4)) in solution was bubbled with argon in an attempt to generate the iron-only mono-carbonyl [((5)L)Fe(II)-CO.Cu(I)](B(C(6)F(5))(4)) species; in coordinating solvent or with axial base present, decreases in characteristic IR-band intensities revealed complete loss of CO from copper and variable loss of CO from the heme.