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Author(s): Timosheva NV; Chandrasekaran A; Holmes RR
Title: Atrane and phosphorane formation with aminotriphenols [1]
Source: ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE 631 (13-14): 2683-2690
Date: 2005
Document Type: Journal : Article
DOI:
Language: English
Comment:
Address: Univ Massachusetts, Dept Chem, Amherst, MA 01003 USA.
Reprint: Holmes, RR, Univ Massachusetts, Dept Chem, Amherst, MA 01003 USA.
E-mail: rrh@chem.umass.edu
Abstract: Reaction of the aminotriphenol, tris (2-hydroxy-3-methyl-5-tert-butylbenzyl)amine, with triphenylphosphite resulted in the formation of the first structurally characterized pentaoxyphosphorane-atrane, N[CH2(Me(t-BU)C6H2)O](3)P(OPh)(2) (1) while reaction of the aminotriphenol, tris (2-hydroxy-3,5-dimethylbenzyl)amine (E) with 2,2'ethylidenebis(4,6-di-tei-t-butylpheiiyl)fluorophosphite led to the isolation of the phosphorane, N[CH2(Me2C6H2)O](2)-P[OC6H2(t-BU)(2)](2)CHCH3 (2), as a result of aminotriphenol to aminodiphenol conversion. X-ray analysis revealed the octahedral geometry of 1 showing strong P-N dative bond coordination (2.114(6) angstrom) and the trigonal bipyramidal arrangement for 2 exhibiting a normal P-N covalent bond (1.652(2) angstrom). H-1, C-13 and P-31 NMR measurements assisted in the structural interpretations and in comparisons with related compounds. The results confirm the premise that donor action at the transition state of active sites of phosphoryl transfer enzymes should enjoy enhanced reaction with nearby donor groups that are positioned to enter into coordination with the reactive phosphoryl component, especially for such enzymatic reactions that exhibit catalytic promiscuity.
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