title: Generation and characterization of [(P)M-(X)-Co(TMPA)]n+ assemblies; P = Porphyrinate, M = FeIII and CoIII, X = O2-, OH-, O2(2-), and TMPA = tris(2-pyridylmethyl)amine.
abstract: With the established chemistry of bridged [(porphyrinate)FeIII-X-CuII(ligand)]n+ [X = O2- (oxo), OH- (hydroxo), O22- (peroxo)] complexes, we investigated the effect of cobalt ion substitution for copper or copper and iron. Thus, in this report, the generation and characterization of new mu-oxo, micro-hydroxo, and micro-peroxo (micro-X) assemblies of [(porphyrinate)MIII-X-CoII/III(TMPA)]n+ assemblies is described, where M = FeIII or CoIII and TMPA = tris(2-pyridylmethyl)amine. The mu-oxo complex [(F8TPP)FeIII-O-CoII(TMPA)]+ (1, F8TPP = tetrakis(2,6-difluorphenyl)porphyrinate) was isolated by an acid-base self-assembly reaction of a 1:1 mixture of (F8TPP)FeIII-OH and [CoII(TMPA)(MeCN)]2+ upon addition of triethylamine. The crystal structure of 1.2C4H10O proved the presence of an unsupported Fe-O-Co moiety; angleFe-O-Co = 171.6 degrees and d(Fe...Co) = 3.58 A. Complex 1 was further characterized by UV-vis (lambdamax = 437 (Soret) and 557 nm), 1H NMR [delta 40.6 (pyrrole-H), 8.8 and 8.7 (m-phenyl-H), 8.0 (p-phenyl-H), 4.4 (PY-4H), 2.6 (PY-3H), 1.0 (PY-5H), -1.1 (PY-6H), and -2.7 (TMPA-CH2-) ppm], electrospray ionization (ESI) and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometric methods, Evans method NMR (microeff = 3.1), and superconducting quantum interference device (SQUID) susceptometry (J = -114 cm-1, S = 1). The micro-hydroxo analogue [(F8TPP)FeIII-(OH)-CoII(TMPA)]+ (2) [UV-vis lambdamax = 567 nm; delta 78 ppm (pyrrole-H); Evans NMR microeff = 3.7] was generated by addition of 1 equiv of triflic acid to 1. The protonation is completely reversible, and 1 is regenerated from 2 by addition of triethylamine. While (F8TPP)FeII/[CoII(TMPA)(MeCN)]2+/O2 chemistry does not lead to a stable micro-peroxo species, a dicobalt micro-peroxo complex [(TPP)CoIII-(O22-)-CoIII(TMPA)]2+ (3, TPP = meso-tetraphenylporphyrinate) forms from a reaction of O2 with a 1:1 mixture of the CoII precursor components at -80 degrees C [UV-vis lambdamax = 435 (Soret), 548, and 583 (weak) nm; silent EPR spectrum; diamagnetic NMR spectrum]. The oxygenation/deoxygenation equilibrium is reversible; warming solutions of 3 releases approximately 1 equiv of O2 and the reduced complexes are reformed.
authors: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors: Eduardo E
authors: EE
authors: Chufan
authors: Claudio N
authors: CN
authors: Verani
authors: Simona C
authors: SC
authors: Puiu
authors: Eva
authors: E
authors: Rentschler
authors: Ulrich
authors: U
authors: Schatzschneider
authors: Christopher
authors: C
authors: Incarvito
authors: Arnold L
authors: AL
authors: Rheingold
authors: Kenneth D
authors: KD
authors: Karlin
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008280:Magnetics; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013237:Stereoisomerism
chemical_list: D009942:Organometallic Compounds; D011725:Pyridines; C431843:tris(2-pyridylmethyl)amine; D003035:Cobalt; D003300:Copper; D007501:Iron; D010100:Oxygen