Our primary aim is to synthesize and determine the geometric and electronic structures of various oxygen-carrying metal complexes which can serve as models of the naturally-occurring blood pigments hemoglobin and myoglobin. Our objective is to obtain from these compounds, by the techniques of X-ray diffraction and infrared spectroscopy quantitative information regarding the geometry of the bound oxygen molecule and detailed data on the changes which occur in the 02 molecule and the metal chelate when they bind together. Such information is essential to a full understanding of the nature of the binding and a quantitative description of the metal-oxygen bond. These concepts, in turn, are necessary if we are to understand oxygen transport in living beings. Initially, we will prepare high-quality single crystals of oxygenated Cobalt Salen derivatives """"""""CoSalen""""""""(Salen = N, N'- ethylenebis(salicylideniminato)) and then expand our efforts to make other oxygenated metal Salen derivatives, such as FeSalen. Specifically, we seek to prepare two series of CoSalen oxygen adducts: those which have identical in-plane ligands but different axial bases, and those which have identical axial bases but different in-plane ligands. Meaningful structural results should then clarify the role of the axial base in the binding of 02 and the effects (if any) that the in-plane substituents have on this interaction. Because the number of combinations of CoSalen substrates, axial bases, solvents, and solution temperatures to be tested will be substantial, a systematic screening process will be set-up to test the products of each reaction for oxygen up-take and crystal-forming propensity. X-ray data will be obtained at liquid nitrogen temperatures and the structures solved by Patterson- Fourier heavy-atom techniques or direct methods. To complete our structural characterization scheme, a correlation of the 0-0 stretching frequencies and 0-0 bond distances will be attempted.

Project Start
Project End
Budget Start
Budget End
Support Year
17
Fiscal Year
1988
Total Cost
Indirect Cost
Name
University of Puerto Rico Rio Piedras
Department
Type
DUNS #
City
San Juan
State
PR
Country
United States
Zip Code
00931
Rodriguez, A D; Ramirez, C; Shi, Y P (2000) The cumbiasins, structurally novel diterpenes possessing intricate carbocyclic skeletons from the West Indian sea whip Pseudopterogorgia elisabethae (Bayer). J Org Chem 65:6682-7
Rodriguez, A D; Ramirez, C (2000) A marine diterpene with a novel tetracyclic framework from the West Indian gorgonian octocoral Pseudopterogorgia elisabethae. Org Lett 2:507-10
Richardson, P L; Rodriguez, A D; Boulanger, A et al. (1998) Methoxyamericanolide B. Acta Crystallogr C 54 ( Pt 1):66-8
Figueroa, I D; el Baraka, M; Quinones, E et al. (1998) A fluorescent temperature probe based on the association between the excited states of 4-(N,N-dimethylamino)benzonitrile and beta-cyclodextrin. Anal Chem 70:3974-7
Rodriguez, A D; Soto, J J (1998) Pseudopterane and norcembrane diterpenoids from the Caribbean sea plume Pseudopterogorgia acerosa. J Nat Prod 61:401-4
Rodriguez, A D; Acosta, A L (1998) New cembranolides from the gorgonian Eunicea succinea. J Nat Prod 61:40-5
Rodriguez, A D; Cobar, O M; Padilla, O L et al. (1997) Calyxamines A and B, novel piperidine alkaloids from the Caribbean sea sponge Calyx podatypa. J Nat Prod 60:1331-3
Cobar, O M; Rodriguez, A D; Padilla, O L (1997) A new steroidal glycoside from a Caribbean gorgonian, Eunicea sp.1. J Nat Prod 60:1186-8
Rodriguez, A D; Gonzalez, E; Huang, S D (1997) Euniciniatin. Acta Crystallogr C 53 ( Pt 3):311-3
Rodriguez, A; Acosta, A L (1997) New cembranoid diterpenes and a geranylgeraniol derivative from the common Caribbean sea whip Eunicea succinea. J Nat Prod 60:1134-8

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