ic020666p_si_001.cif (146.32 kB)
Influence of Hydrogen Bonding in Competition with Lattice Interactions on Carbonyl Coordination at Phosphorus. Implications for Phosphoryl Transfer Activated States1
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posted on 2003-04-12, 00:00 authored by A. Chandrasekaran, Natalya V. Timosheva, Roberta O. Day, Robert R. HolmesA series of phosphorus compounds containing carboxyl groups that serve as mimics for amino acid residues was
synthesized. The series was composed of the phosphonium salts 1A, 1B, and 2, the anionic phosphines 3A and
3B, and the anionic phosphine oxide 4. X-ray structural analysis revealed that P−O coordination occurred in the
presence of extensive hydrogen bonding and led to pseudo or regular trigonal bipyramidal geometries. 31P chemical
shifts indicated retention of the basic coordination geometries in solution. The two forms observed for 1 and 3
revealed the influence of hydrogen bonding on the P−O donor interactions while 2 and 4 showed the influence of
molecular packing effects in competition with hydrogen bonding interactions. The results suggest that phosphoryl
transfer enzyme mechanisms should benefit by taking into account P−O donor interactions by residues at active
sites that can be manipulated by hydrogen bonding and molecular packing effects in enhancing nucleophilic attack
at phosphorus centers.
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coordination geometries31 P chemical shiftsdonorphosphoryl transfer enzyme mechanismsacid residuesphosphine oxide 4phosphorus centersseriesnucleophilic attackHydrogen Bondinginfluence1 BLattice Interactionsphosphines 3phosphonium salts 1interactionCarbonyl Coordination3 Bcarboxyl groupsphosphorus compoundsbipyramidal geometriesPhosphoryl Transfer Activated States 1
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