| Autor: |
Pokhriyal D; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., Heins SP; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., Sifri RJ; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., Gentekos DT; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., Coleman RE; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., Wolczanski PT; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., Cundari TR; Department of Chemistry, CASCaM, University of North Texas, Denton, Texas 76201, United States., Fors BP; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., Lancaster KM; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States., MacMillan SN; Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York, 14853, United States. |
| Abstrakt: |
The exploration of pyridine-imine (PI) iron complexes that exhibit redox noninnocence (RNI) led to several interesting discoveries. The reduction of (PI)FeX 2 species afforded disproportionation products such as (dmpPI) 2 FeX (dmp = 2,6-Me 2 -C 6 H 3 , X = Cl, Br; 8 -X) and (dippPI) 2 FeX (dipp = 2,6- i Pr 2 -C 6 H 3 , X = Cl, Br; 9 -X), which were independently prepared by reductions of (PI)FeX 2 in the presence of PI. The crystal structure of 8 -Br possessed an asymmetric unit with two distinct electromers, species with different electronic GSs: a low-spin ( S = 1/2) configuration derived from an intermediate-spin S = 1 core antiferromagnetically (AF) coupled to an S = 1/2 PI ligand, and an S = 3/2 center resulting from a high-spin S = 2 core AF-coupled to an S = 1/2 PI ligand. Calculations were used to energetically compare plausible ground states. Polydentate diazepane-PI (DHPI) ligands were applied to the synthesis of monomeric dihalides (DHPI)FeX 2 (X = Cl, 1 -Cl 2 ; X = Br, 1 -Br 2 ); reduction generated the highly distorted bioctahedral dimers (DHPA) 2 Fe 2 X 2 (( 3 -X) 2 ) containing a C-C bond formed from imine coupling; the monomers 1 -X 2 could be regenerated upon Ph 3 CX oxidation. Dihalides and their reduced counterparts were subjected to various alkyl halides and methyl methacrylate (MMA), generating polymers with little to no molecular weight control, indicative of simple radical-initiated polymerization. |
