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Phosphonate-substituted zirconium oxo clusters.

Czakler M, Schubert U - Monatsh. Chem. (2015)

Bottom Line: The phosphonate-substituted zirconium oxo clusters Zr6O2(OBu)12(O3PPh)4 and Zr7O2(OiPr)12(O3PCH2CH2CH2Br)6, with octahedrally coordinated Zr atoms, were synthesized by reaction of zirconium alkoxides with phosphonic acid bis(trimethylsilyl) esters.The basic structural motif are Zr3O(µ2-OR)3(OR)3 units which are connected in different ways.

View Article: PubMed Central - PubMed

Affiliation: Institute of Materials Chemistry, Vienna University of Technology, Vienna, Austria.

ABSTRACT

Abstract: The phosphonate-substituted zirconium oxo clusters Zr6O2(OBu)12(O3PPh)4 and Zr7O2(OiPr)12(O3PCH2CH2CH2Br)6, with octahedrally coordinated Zr atoms, were synthesized by reaction of zirconium alkoxides with phosphonic acid bis(trimethylsilyl) esters. The basic structural motif are Zr3O(µ2-OR)3(OR)3 units which are connected in different ways.

No MeSH data available.


Molecular structure of Zr7O2(µ2-OiPr)6(OiPr)6(O3PCH2CH2CH2Br)6 (2). Hydrogen atoms are omitted for clarity. Selected bond lengths/pm and angles/°: O(1)-Zr(1) 207.9(4), O(1)-Zr(2) 209.3(4), O(1)-Zr(3) 208.2(4), O(2)-Zr(5) 208.9(4), O(2)-Zr(6) 209.2(4), O(2)-Zr(7) 208.8(4), O(5)-Zr(2) 216.4(4), O(5)-Zr(3) 217.0(4), O(7)-Zr(5) 218.6(4), O(7)-Zr(7) 216.5(5), O(9)-Zr(1) 194.2(5), O(10)-Zr(2) 193.1(5), O(13)-Zr(6) 192.2(5), O(18)-Zr(1) 210.1(4), O(21)-Zr(2) 211.7(4), O(23)-Zr(4) 206.0(4), O(25)-Zr(6) 211.1(4), O(26)-Zr(4) 207.4(4), O(28)-Zr(7) 210.6(5); Zr(1)-O(1)-Zr(2) 108.09(18), Zr(7)-O(7)-Zr(5) 101.9(2)
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Fig2: Molecular structure of Zr7O2(µ2-OiPr)6(OiPr)6(O3PCH2CH2CH2Br)6 (2). Hydrogen atoms are omitted for clarity. Selected bond lengths/pm and angles/°: O(1)-Zr(1) 207.9(4), O(1)-Zr(2) 209.3(4), O(1)-Zr(3) 208.2(4), O(2)-Zr(5) 208.9(4), O(2)-Zr(6) 209.2(4), O(2)-Zr(7) 208.8(4), O(5)-Zr(2) 216.4(4), O(5)-Zr(3) 217.0(4), O(7)-Zr(5) 218.6(4), O(7)-Zr(7) 216.5(5), O(9)-Zr(1) 194.2(5), O(10)-Zr(2) 193.1(5), O(13)-Zr(6) 192.2(5), O(18)-Zr(1) 210.1(4), O(21)-Zr(2) 211.7(4), O(23)-Zr(4) 206.0(4), O(25)-Zr(6) 211.1(4), O(26)-Zr(4) 207.4(4), O(28)-Zr(7) 210.6(5); Zr(1)-O(1)-Zr(2) 108.09(18), Zr(7)-O(7)-Zr(5) 101.9(2)

Mentions: A zirconium oxo cluster isostructural to Ti7O2(OiPr)12(O3PR)6, viz. Zr7O2(µ2-OiPr)6(OiPr)6(O3PCH2CH2CH2Br)6 (2, Fig. 2), was, however, obtained in another experiment, i.e., reaction of Zr(OiPr)4 with bis(trimethyl)silyl(3-bromopropyl)phosphonate, methacrylic acid, and water. Since water generation by esterification of phosphonic acid (as in the first experiment) is relatively slow, water was deliberately added. Methacrylic acid was added anticipating an oxo cluster with a mixed ligand sphere as had been the case for analogous reactions with Ti(OR)4 [15, 17]. No mixed ligand cluster was obtained, however, in the reaction of Zr(OiPr)4.Fig. 2


Phosphonate-substituted zirconium oxo clusters.

Czakler M, Schubert U - Monatsh. Chem. (2015)

Molecular structure of Zr7O2(µ2-OiPr)6(OiPr)6(O3PCH2CH2CH2Br)6 (2). Hydrogen atoms are omitted for clarity. Selected bond lengths/pm and angles/°: O(1)-Zr(1) 207.9(4), O(1)-Zr(2) 209.3(4), O(1)-Zr(3) 208.2(4), O(2)-Zr(5) 208.9(4), O(2)-Zr(6) 209.2(4), O(2)-Zr(7) 208.8(4), O(5)-Zr(2) 216.4(4), O(5)-Zr(3) 217.0(4), O(7)-Zr(5) 218.6(4), O(7)-Zr(7) 216.5(5), O(9)-Zr(1) 194.2(5), O(10)-Zr(2) 193.1(5), O(13)-Zr(6) 192.2(5), O(18)-Zr(1) 210.1(4), O(21)-Zr(2) 211.7(4), O(23)-Zr(4) 206.0(4), O(25)-Zr(6) 211.1(4), O(26)-Zr(4) 207.4(4), O(28)-Zr(7) 210.6(5); Zr(1)-O(1)-Zr(2) 108.09(18), Zr(7)-O(7)-Zr(5) 101.9(2)
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Fig2: Molecular structure of Zr7O2(µ2-OiPr)6(OiPr)6(O3PCH2CH2CH2Br)6 (2). Hydrogen atoms are omitted for clarity. Selected bond lengths/pm and angles/°: O(1)-Zr(1) 207.9(4), O(1)-Zr(2) 209.3(4), O(1)-Zr(3) 208.2(4), O(2)-Zr(5) 208.9(4), O(2)-Zr(6) 209.2(4), O(2)-Zr(7) 208.8(4), O(5)-Zr(2) 216.4(4), O(5)-Zr(3) 217.0(4), O(7)-Zr(5) 218.6(4), O(7)-Zr(7) 216.5(5), O(9)-Zr(1) 194.2(5), O(10)-Zr(2) 193.1(5), O(13)-Zr(6) 192.2(5), O(18)-Zr(1) 210.1(4), O(21)-Zr(2) 211.7(4), O(23)-Zr(4) 206.0(4), O(25)-Zr(6) 211.1(4), O(26)-Zr(4) 207.4(4), O(28)-Zr(7) 210.6(5); Zr(1)-O(1)-Zr(2) 108.09(18), Zr(7)-O(7)-Zr(5) 101.9(2)
Mentions: A zirconium oxo cluster isostructural to Ti7O2(OiPr)12(O3PR)6, viz. Zr7O2(µ2-OiPr)6(OiPr)6(O3PCH2CH2CH2Br)6 (2, Fig. 2), was, however, obtained in another experiment, i.e., reaction of Zr(OiPr)4 with bis(trimethyl)silyl(3-bromopropyl)phosphonate, methacrylic acid, and water. Since water generation by esterification of phosphonic acid (as in the first experiment) is relatively slow, water was deliberately added. Methacrylic acid was added anticipating an oxo cluster with a mixed ligand sphere as had been the case for analogous reactions with Ti(OR)4 [15, 17]. No mixed ligand cluster was obtained, however, in the reaction of Zr(OiPr)4.Fig. 2

Bottom Line: The phosphonate-substituted zirconium oxo clusters Zr6O2(OBu)12(O3PPh)4 and Zr7O2(OiPr)12(O3PCH2CH2CH2Br)6, with octahedrally coordinated Zr atoms, were synthesized by reaction of zirconium alkoxides with phosphonic acid bis(trimethylsilyl) esters.The basic structural motif are Zr3O(µ2-OR)3(OR)3 units which are connected in different ways.

View Article: PubMed Central - PubMed

Affiliation: Institute of Materials Chemistry, Vienna University of Technology, Vienna, Austria.

ABSTRACT

Abstract: The phosphonate-substituted zirconium oxo clusters Zr6O2(OBu)12(O3PPh)4 and Zr7O2(OiPr)12(O3PCH2CH2CH2Br)6, with octahedrally coordinated Zr atoms, were synthesized by reaction of zirconium alkoxides with phosphonic acid bis(trimethylsilyl) esters. The basic structural motif are Zr3O(µ2-OR)3(OR)3 units which are connected in different ways.

No MeSH data available.