Presentation Title

Square planar Cu(I) complexes with geometric constraints pertinent to copper proteins

Presentation Type

Poster

Abstract

The fast electron transfer (ET) in Type 1 copper proteins is recognized and attributed to the highly constrained copper sites. Known as the “rack” or “entatic” states, the distorted active site geometries are adapted to minimize reorganization energies when switching between oxidation states. To understand the structural contribution to ET rates, a family of the highly constrained square planar Cu (I) complexes were synthesized. Although unusual for the d10 configuration, monomeric square planar Cu (I) compounds are synthetically accessible by using pincer-type pyridinediimine (PDI) ligands. X-ray crystallographic data revealed that the PDICu (I) compounds were distorted square planar with τ4 values close to 0. The reorganization of the geometry between the Cu (I/II) states was quantified by the ∆τ4 parameter. Further, the ∆τ4 parameters were correlated to the self-exchange rate constants of the PDI Cu complexes derived from the NMR line broadening experiments. Compared to other Cu systems with N donor, square planar Cu complexes are capable of faster electron transfer.

Start Date

6-5-2017 12:15 PM

End Date

6-5-2017 2:00 PM

Location

Miller Hall

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May 6th, 12:15 PM May 6th, 2:00 PM

Square planar Cu(I) complexes with geometric constraints pertinent to copper proteins

Miller Hall

The fast electron transfer (ET) in Type 1 copper proteins is recognized and attributed to the highly constrained copper sites. Known as the “rack” or “entatic” states, the distorted active site geometries are adapted to minimize reorganization energies when switching between oxidation states. To understand the structural contribution to ET rates, a family of the highly constrained square planar Cu (I) complexes were synthesized. Although unusual for the d10 configuration, monomeric square planar Cu (I) compounds are synthetically accessible by using pincer-type pyridinediimine (PDI) ligands. X-ray crystallographic data revealed that the PDICu (I) compounds were distorted square planar with τ4 values close to 0. The reorganization of the geometry between the Cu (I/II) states was quantified by the ∆τ4 parameter. Further, the ∆τ4 parameters were correlated to the self-exchange rate constants of the PDI Cu complexes derived from the NMR line broadening experiments. Compared to other Cu systems with N donor, square planar Cu complexes are capable of faster electron transfer.