Tethered pyrazolyl phosphinate: pyrazolyl-N- and phosphoryl-O-metal coordination in Ph2P(O){OCH2CH2(3,5-Me2Pz)}

Chandrasekhar, Vadapalli ; Kingsley, Savariraj ; Incarvito, Christopher D. ; Lam, Matthew K. ; Rheingold, Arnold L. (2001) Tethered pyrazolyl phosphinate: pyrazolyl-N- and phosphoryl-O-metal coordination in Ph2P(O){OCH2CH2(3,5-Me2Pz)} Inorganic Chemistry, 40 (23). pp. 5890-5896. ISSN 0020-1669

Full text not available from this repository.

Official URL: http://pubs.acs.org/doi/abs/10.1021/ic010454c

Related URL: http://dx.doi.org/10.1021/ic010454c

Abstract

Phosphorus pyrazolides, P(O)(3,5-Me2Pz)3 or RP(E)(3,5-Me2Pz)2 [E = S or O, R = Me or Ph], are hydrolytically sensitive particularly upon interaction with transition metal ions. In this paper, we report a new tethered pyrazolyl phosphinate, Ph2P(O){OCH2CH2(3,5-Me2Pz)} DPEP (1), where the pyrazolyl group is separated from the phosphorus by means of an ethyleneoxy spacer. 1 has two potential coordination sites in the form of a phosphoryl oxygen atom and a pyrazolyl nitrogen atom. 1 forms hydrolytically stable complexes, (DPEP·CoCl2)n (2), (DPEP)2·CuCl2 (3), (DPEP·ZnCl2)n (4), and (DPEP)2·PdCl2 (5). The cobalt(II) and the zinc(II) complexes 2 and 4 show a zigzag polymeric structure in the solid state with a tetrahedral coordination geometry around the metal ion; the ligand DPEP coordinates through its phosphoryl oxygen and the pyrazolyl nitrogen to two neighboring metal ions and functions as a bridging ligand to form the polymeric structure. In contrast to 2 and 4, the copper(II) and the palladium(II) complexes 3 and 5 show a square-planar geometry around the metal ion. Exclusive coordination through the pyrazolyl nitrogens of the ligand 1 is observed. An extensive supramolecular sheetlike two-dimensional polymeric network is observed in the solid-state structures of 3 and 5 as a result of two weak interactions: (a) an intermolecular C-H---O interaction involving the phosphoryl oxygen and an aromatic C-H and (b) a p-p face-to-face stacking interaction between the phenyl groups of two adjacent molecules.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:8947
Deposited On:28 Oct 2010 10:29
Last Modified:28 Oct 2010 10:29

Repository Staff Only: item control page