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Di-, tri-, tetra-, and hexanuclear copper(ii) mono-organophosphates: structure and nuclearity dependence on the choice of phosphorus substituents and auxiliary n-donor ligands

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Title Di-, tri-, tetra-, and hexanuclear copper(ii) mono-organophosphates: structure and nuclearity dependence on the choice of phosphorus substituents and auxiliary n-donor ligands
 
Creator MURUGAVEL, R
KUPPUSWAMY, S
MAITY, AN
SINGH, MP
 
Subject tert-butyl phosphate
x-ray-structure
source molecular precursors
crystal-structure
phosphodiester hydrolysis
magnetic-behavior
metal-phosphonate
monoester binding
bridging ligands
pyrazole ligands
 
Description Reactions of 2,6-dimethylphenyl phosphate (dmppH(2)) and 2,6-diisopropylphenyl phosphate (dippH(2)) with copper(II) precursors have been investigated in the presence of auxiliary N-donor ligands, and new structural types of copper phosphates have been isolated. Copper acetate reacts with dmppH2 in the presence of either 3,5-di-tert-butyl pyrazole (dbpz) or 3,5-dimethyl pyrazole (dmpz), leading to the isolation of tetrameric complex [Cu(dmpp)(dbpz)](4) 1 and hexanuclear cage complex [Cu(6)(PO(4))(dmpp)(3)(OAc)(3)(dmpz)(9)] 2, respectively. Whereas compound 1 is a cubane-shaped cluster whose Cu(4)O(12)P(4) core resembles the double-4-ring (D4R) zeolite SBU, compound 2 is a novel hexanuclear copper complex with an unprecedented structure in metal phosphate chemistry. Use of bulkier dippH(2) in the above reactions, however, yielded metal-free acid-base complexes [(dippH)(dbpz)(dbpzH)] 3 and [(dippH)(dmpz)(dmpzH)] 4, respectively. The reactions carried out between copper acetate and dmppH2 or dippH(2) in the presence of chelating ligand 1,10-phenanthroline produced structurally similar dimeric copper phosphates [Cu(phen)(dmpp)(CH(3)OH)](2) center dot 2CH(3)OH 5 and [Cu(phen)(dipp)(CH(3)OH)](2) center dot 2CH(3)OH 6 with a S4R SBU core. Changing the copper source to [Cu(2)(bpy)(2)(OAc)(OH)(H(2)O)] center dot 2CIO(4) and carrying out reactions both with dippH(2) and with dmppH(2) result in the formation of trinuclear copper phosphates [Cu(3)(bpy)(3)(dmpp)(2)(CH(3)OH)(3)] center dot 2ClO(4) center dot 2CH(3)OH 7 and [Cu(3)(bpy)(3)(dipp)(2)(CH(3)OH)(3)] center dot 2ClO(4) center dot 2CH(3)OH 8. The three copper ions in 7 and 8 are held together by two bridging phosphate ligands to produce a tricyclic derivative whose core resembles the 4=1 SBU of zeolites. Compounds 1-8 have been characterized by elemental analysis and IR, absorption, emission, and EPR spectroscopic techniques. The crystal structures of compounds 1, 2, 4, 5, 6, and 8 have also been established by single-crystal X-ray diffraction studies.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-10-15T07:57:22Z
2011-12-15T09:16:24Z
2011-10-15T07:57:22Z
2011-12-15T09:16:24Z
2009
 
Type Review
 
Identifier INORGANIC CHEMISTRY,48(1)183-192
0020-1669
http://dx.doi.org/10.1021/ic801532y
http://dspace.library.iitb.ac.in/xmlui/handle/10054/13955
http://hdl.handle.net/100/3147
 
Language en