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Selective Phosphoramidite Cleavage as a Route to Novel Chiral and Achiral Pentacoordinated Nickel(II) PNP Pincer Complexes
Author(s) -
BenitoGaragorri David,
Mereiter Kurt,
Kirchner Karl
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600498
Subject(s) - chemistry , phosphinite , phosphoramidite , pincer movement , ligand (biochemistry) , pincer ligand , medicinal chemistry , anhydrous , stereochemistry , nickel , bond cleavage , catalysis , organic chemistry , receptor , dna , biochemistry , oligonucleotide
Treatment of NiBr 2 (DME) (DME = 1,2‐dimethoxyethane) or anhydrous NiBr 2 with 2 equiv. of PNP pincer ligands featuring phosphoramidites in CH 2 Cl 2 yields the novel neutral pentacoordinate complexes [Ni(PNP){κ 1 (P)‐R 2 P=O}Br]. Over the course of this reaction the P–N bonds of the phosphoramidite units of one PNP ligand are selectively cleaved due to hydrolysis affording an anionic κ 1 ‐(P)‐coordinated phosphinite ligand [R 2 P=O] – , while a second PNP ligand remains intact and is coordinated in a κ 3 ‐(P,N,P) fashion. The X‐ray structure of one [Ni(PNP){κ 1 (P)‐PR 2 =O}Br] complex has been determined.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)