The synthesis and characterization of various borylated bis(dimethylglyoximato)iron complexes, Fe(DMGBR(2))(2-) LL’ (BR(2) = BH2, BF2, BPh(2), or BBN (9-borabicyclo[3.3.1]nonane) and axial ligands L or L’ pyridine, 1-methylimidazole, CO, butylamine, nitriles, NH3, etc.) are described. Carbonyl complexes crystallize in the C-2 nu conformation with both axial boron groups on the CO binding face. The bis(butylamine) complexes all show a C-2h conformation. mash photolysis studies of the carbonyl complexes and ligand substitution kinetics of other derivatives probe the linkage between the conformational dynamics of the macrocycle and the ligational. dynamics of the iron complex. On-rate effects produced by groups which block access to the iron are compared with those for hemoproteins and superstructured hemes. Off-rate constants are largely unrelated to bond lengths or pi-bonding/charge transfer effects. The off-rates reflect the true coordinate bond energy while structural and spectroscopic data only measure local phenomena. Electrochemical studies of Fe(DMGBR(2))(2)(PY)(2) complexes and the nitrile complexes Fe(DMGBPh(2))(2)(PY)(RCN), RCN = 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetracyanoethylene (TCNE), are described.