Sterically encumbered acyclic diphosphazanes: synthesis, conformations and coordination behavior

Prabusankar, Ganesan ; Palanisami, Nallasamy ; Murugavel, Ramaswamy ; Butcher, Ray J. (2006) Sterically encumbered acyclic diphosphazanes: synthesis, conformations and coordination behavior Dalton Transactions, 2006 (17). pp. 2140-2146. ISSN 1477-9226

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Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/2006...

Related URL: http://dx.doi.org/10.1039/B516316A

Abstract

The reaction between λ 3-diphosphazane [EtN(PCl2)2] and the sodium salts of substituted phenols affords sterically encumbered diphosphazanes [EtN{P(OR)2}2] (R = -C6H3iPr2-2,6 (1), -C6H3Me2-2,6 (2) and -C6H2Me3-2,4,6 (3)). When the same reaction was carried out with bulky sodium 2,4-di-tert-butyl-4-methylphenoxide, only a monosubstitution takes place to result in the formation of [EtN{PCl(OR)}2] (R = -C6H2tBu2-2,6-Me-4) (4). Further reaction of 2 with [Mo(CO)4(NBD)] produces cis-[(EtN{P(OC6H3Me2-2,6)2}2)Mo(CO)4] (5). Diphosphazanes 1-4 and the metal derivative 5 have been characterized by means of their analytical data and EI-MS, IR and multinuclear NMR (1H and 31P) spectral data. The solid-state structure of the diphosphazanes 1, 2 and 4, and the molybdenum complex 5 have been determined by X-ray diffraction studies. Irrespective of the size of substituent, the bulky groups on the phosphorus and nitrogen are on the same side of the P-N-P skeleton with a local C2v symmetry. The central nitrogen remains almost trigonal planar in all the compounds.

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