Hexacoordinate Phosphorus via Donor Interaction. Implications Regarding Enzymatic Reaction Intermediates

Abstract

as Professor of Inorganic Chemistry. His publications number over 230 and include two invited ACS monographs, Nos. 175 and 176, on pentacoordinated phosphorus. His wife, Joan, is a chemist who is a coauthor on many of his publications. Currently, he is Editor-in-Chief of Phosphorus, Sulfur, and Silicon and the Related Elements and Editor of Main Group Chemistry News.

The isomeric structure of pentacoordinate chiral spirophosphoranes in solution by the combined use of NMR experiments and GIAO DFT calculations of NMR parameters

“…[39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][57][58][59][60] At the same time the examples of application of these approaches on phosphorus are rather sparse. [54][55][56] We used a combination (PBE1PBE/6-311G(2d,2p)//PBE1PBE/ 6-31+G(d)) that proved to be reliable and effective for 31 P NMR CS calculations. First, the geometry optimization in the frames of the DFT (PBE1PBE/6-31+G(d)) method predicts that these three main isomers are close in energy (Table 1).…”

“…enzymatic phosphoryl transfer reactions, hydrolysis/formation of DNA, RNA, cyclic AMP). 30,31 Their structural and dynamic properties strongly correlate with the reactivity/selectivity of the processes they are involved in. Although the knowledge about the stereochemistry (the absolute and relative configurations) of these compounds is important in understanding these processes, very few structural studies of pentacoordinate phosphorus systems have been published so far.…”

“…There are a number of examples when DFT calculations of NMR 1 H, 13 C and 15 N parameters in the frame of the GIAO method allowed the establishment of tautomeric, isomeric and conformational structures as well. [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] However applications of similar approaches to analyze phosphorus compounds by DFT calculations of 31 P NMR parameters are very rare. [54][55][56] The study here shows that the interplay of the NMR experiment and theory is a powerful method for determining the relative configurations of pentacoordinate chiral spirophosphoranes.…”

New Trends in Hexacoordinated Phosphorus Chemistry

“…This field of phosphorus chemistry was extensively reviewed, most recently by Cavell and Holmes [6][7][8], and only novel structures since 1996 are detailed. A different approach to the generation of neutral P(VI) adducts consists in the generation of dinuclear zwitterionic l -) species.…”

“…Since this discovery, and now for more than 40 years, chemists interested in organic, inorganic, physical, and applied chemistry have generated compounds based on hexacoordinated phosphorus and studied these many derivatives for a variety of applications. Earlier work was reviewed in 1972 by Hellwinkel [5] and more recent articles are those of Cavell [6] and Holmes [7,8]. Several manuscripts or book chapters have also been written on the topic giving a good -yet slightly outdated -overview of the field [9][10][11][12].…”