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Di-tert-butyl phosphate complexes of cobalt(II) and zinc(II) as precursors for ceramic M(PO(3))(2) and M(2)P(2)O(7) materials: Synthesis, spectral characterization, structural studies, and role of auxiliary ligands

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Title Di-tert-butyl phosphate complexes of cobalt(II) and zinc(II) as precursors for ceramic M(PO(3))(2) and M(2)P(2)O(7) materials: Synthesis, spectral characterization, structural studies, and role of auxiliary ligands
 
Creator MURUGAVEL, R
SATHIYENDIRAN, M
WALAWALKAR, MG
 
Subject crystal-structure
di(tert-butyl)phosphate complexes
alkoxysiloxy derivatives
molecular-structure
aluminum phosphate
metal-oxides
silica
chemistry
routes
model
 
Description Reaction of the metal acetates M(OAc)(2). xH(2)O with di-tert-butyl phosphate (dtbp-H) (3) in a 4:6 molar ratio in methanol or tetrahydrofuran followed by slow evaporation of the solvent results in the formation of metal phosphate clusters [M(4)(mu (4)-O)(dtbp)(6)] (M = Co (4, blue); Zn (5, colorless)) in nearly quantitative yields. The same reaction, when carried out in the presence of a donor auxiliary ligand such as imidazole (imz) and ethylenediamine (en), results in the formation of octahedral complexes [M(dtbp)(2)(imz)(4)] (M = Co (6); Ni (7); Zn (8)) and [Co(dtbp)(2)-(en)(2)] (9). The tetrameric clusters 4 and 5 could also be converted into mononuclear 6 and 8, respectively, by treating them with a large excess of imidazole. The use of slightly bulkier auxiliary ligand 3,5-dimethylpyrazole (3,5-dmp) in the reaction between cobalt acetate and 3 results in the isolation of mononuclear tetrahedral complex [Co(dtbp)(2)(3,5-dmp)(2)] (10) in nearly quantitative yields. Perfectly air- and moisture-stable samples of 4-10 were characterized with the aid of analytical, thermoanalytical, and spectroscopic techniques. The molecular structures of the monomeric pale-pink compound 6, colorless 8, and deep-blue 10 were further established by single-crystal X-ray diffraction studies. Crystal data for 6: C(28)H(52)CoN(8)O(8)P(2), a = 8.525(1) Angstrom, b = 9.331(3) Angstrom, c = 12.697(2) Angstrom, alpha = 86.40(2)degrees, beta = 88.12(3)degrees, gamma = 67.12(2)degrees, triclinic, P (1) over bar, Z = 1. Crystal data for 8: C(28)H(52)N(8)O(8)P(2)Zn, a = 8.488(1) Angstrom, b = 9.333(1) Angstrom, c = 12.723(2) Angstrom, alpha = 86.55(1)degrees, beta = 88.04(1)degrees, gamma = 67.42(1)degrees, triclinic, P (1) over bar, Z = 1. Crystal data for 10: C(26)H(52)CON(4)O(8)P(2), a = b = 18.114(1) Angstrom, c = 10.862(1) Angstrom, tetragonal, P4(1), Z = 4. The Co(2+) ion in 6 is octahedrally coordinated by four imidazole nitrogens which occupy the equatorial positions and oxygens of two phosphate anions on the axial coordination sites. The zinc derivative 8 is isostructural to the cobalt derivative 6. The crystal structure of 10 reveals that the central cobalt atom is tetrahedrally coordinated by two phosphate and two 3,5-dmp ligands. In all structurally characterized monomeric compounds (6, 8, and 10), the dtbp ligand acts as a monodentate, terminal ligand with free P=O phosphoryl groups. Thermal studies indicate that heating the samples at 171 (for 4) or 93 degreesC (for 5) leads to the loss of twelve equivalents of isobutene gas yielding carbon-free [M(4)(mu (4)-O)(O(2)P(OH)(2))(6)], which undergoes further condensation by water elimination to yield a material of the composition Co(4)O(19)P(6) This sample of 4 when heated above 500 degreesC contains the crystalline metaphosphate Co(PO(3))(2) along with amorphous pyrophosphate M(2)P(2)O(7) in a 2:1 ratio. Similar heat treatment on samples 6-8 results in the exclusive formation of the respective metaphosphates Co(PO(3))(2), Ni(PO(3))(2), and Zn(PO(3))(2); the tetrahedral derivative 10 also cleanly converts into Co(PO(3))(2) On heating above 600 degreesC.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-13T23:00:08Z
2011-12-26T12:47:26Z
2011-12-27T05:52:02Z
2011-07-13T23:00:08Z
2011-12-26T12:47:26Z
2011-12-27T05:52:02Z
2001
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 40(3), 427-434
0020-1669
http://dx.doi.org/10.1021/ic0006100
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3795
http://hdl.handle.net/10054/3795
 
Language en