Tris(organozinc) Phosphazenates as Templates for Trimeric and Hexameric Zinc Oxide Clusters^†

Ramamoorthy Boomishankar Dr.,

Ramamoorthy Boomishankar Dr.

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK, Fax: (+44) 151-794-388

Search for more papers by this author

Philip I. Richards Dr.,

Philip I. Richards Dr.

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK, Fax: (+44) 151-794-388

Search for more papers by this author

Alexander Steiner Dr.,

Alexander Steiner Dr.

[email protected]

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK, Fax: (+44) 151-794-388

Search for more papers by this author

Ramamoorthy Boomishankar Dr.,

Ramamoorthy Boomishankar Dr.

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK, Fax: (+44) 151-794-388

Search for more papers by this author

Philip I. Richards Dr.,

Philip I. Richards Dr.

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK, Fax: (+44) 151-794-388

Search for more papers by this author

Alexander Steiner Dr.,

Alexander Steiner Dr.

[email protected]

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK, Fax: (+44) 151-794-388

Search for more papers by this author

First published: 03 July 2006

https://doi.org/10.1002/anie.200601138

Citations: 36

^†

This work was supported by EPSRC.

Share a link

Email
Wechat
Bluesky

Graphical Abstract

Casting clusters from the mold: Tris(ethylzinc) phosphazenates exhibit a bowl-shaped coordination surface of three Lewis acidic EtZn moieties and three Lewis basic N sites. This surface provides a perfect mold for planar {(ZnO)₃} rings and hexagonal {(ZnO)₆} prisms. The zinc oxide clusters were generated in situ by reaction of phosphazene hydrates with diethylzinc.

References

1
1aJ.-P. Jolivet, Metal Oxide Chemistry and Synthesis: From Solution to Solid State, Wiley, Chichester, 2000;
Google Scholar
1bC. N. R. Rao, B. Raveau, Transition Metal Oxides: Structure, Properties, and Synthesis of Ceramic Oxides, Wiley-VCH, Weinheim, 1998;
Google Scholar
1cJ. M. Thomas, W. J. Thomas, Principles and Practice of Heterogeneous Catalysis, Wiley-VCH, Weinheim, 1997.
Google Scholar
2
2aH. W. Roesky, I. Haiduc, N. S. Hosmane, Chem. Rev. 2003, 103, 2579;
10.1021/cr020376q
CAS PubMed Web of Science® Google Scholar
2bH. W. Roesky, M. G. Walawalkar, R. Murugavel, Acc. Chem. Res. 2001, 34, 201;
10.1021/ar0001158
CAS PubMed Web of Science® Google Scholar
2cV. Chandrasekhar, S. Nagendran, V. Baskar, Coord. Chem. Rev. 2002, 235, 1.
10.1016/S0010-8545(02)00178-9
CAS Web of Science® Google Scholar
3A. E. H. Wheatley, Chem. Soc. Rev. 2001, 30, 265.
10.1039/b101276m
CAS Web of Science® Google Scholar
4A. M. Drummond, L. T. Gibson, A. R. Kennedy, R. E. Mulvey, C. T. O'Hara, R. B. Rowlings, T. Weightman, Angew. Chem. 2002, 114, 2488;
10.1002/1521-3757(20020703)114:13<2488::AID-ANGE2488>3.0.CO;2-A
Google Scholar
Angew. Chem. Int. Ed. 2002, 41, 2382.
10.1002/1521-3773(20020703)41:13<2382::AID-ANIE2382>3.0.CO;2-B
CAS PubMed Web of Science® Google Scholar
5A. Steiner, S. Zacchini, P. I. Richards, Coord. Chem. Rev. 2002, 227, 193.
10.1016/S0010-8545(02)00012-7
CAS Web of Science® Google Scholar
6G. T. Lawson, F. Rivals, M. Tascher, C. Jacob, J. F. Bickley, A. Steiner, Chem. Commun. 2000, 341.
10.1039/a908954c
CAS Web of Science® Google Scholar
7Crystal data were measured on a Bruker Apex diffractometer at T=100 K using Mo_Kα radiation. Crystal structures were refined against F² using all data.^[14] 2: C₄₈H₁₂₀N₁₈P₆Zn₆, M_r=1527.7, C2/c, a=22.0843(11), b=13.8929(7), c=23.6468(12) Å, β=95.3500(10)°, V=7223.6(6) Å³, Z=4, R1 (I>2σ(I))=0.028, wR2 (all data)=0.074; 3: C₄₈H₁₂₀N₁₈O₃P₆Zn₉, M_r=1771.8, P2₁/c, a=16.5237(9), b=15.2248(9), c=29.8265(17) Å, β=91.7800(10)°, V=7499.8(7) Å³, Z=4, R1 (I>2σ(I))=0.038, wR2 (all data)=0.100; 5⋅1.5 C₆H₁₄: C₉₃H₁₈₉N₁₈O₆P₆Zn₁₂, M_r=2625.9, P, a=14.164(2), b=14.976(2), c=16.602(2) Å, α=113.405(2), β=100.528(3), γ=96.041(2)°, V=3115.2(8) Å³, Z=1, R1 (I>2σ(I))=0.035, wR2 (all data)=0.102; 7: C₆₀H₁₄₄N₁₈O₆P₆Zn₆, M_r=1940.1, Rc, a=18.8839(10), c=50.977(6) Å, V=15 743(2) Å³, Z=6, R1 (I>2σ(I))=0.099, wR2 (all data)=0.35. Crystals of 7 diffracted very weakly and refined poorly, thus structural parameters are not discussed; however, the data quality was sufficient to confirm the connectivity of 7. Crystallographic data in CIF format (CCDC-602267 (2), -602268 (3), -602269 (5), -602266 (7)) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Google Scholar
8A detailed account on phosphazene hydrates will be reported elsewhere. Selected data for 1⋅1.5 H₂O: m.p. 55 °C, P2₁/n, a=9.3162(5), b=24.704(1), c=24.810(1) Å, β=92.460(1)°; 4⋅5 H₂O: m.p. 162 °C, P2₁/n, a=16.736(3), b=19.977(2), c=27.476(3) Å, β=104.46(2)°.
Google Scholar
9I. B. Gorrell, A. Looney, G. Parkin, A. L. Rheingold, J. Am. Chem. Soc. 1990, 112, 4068.
10.1021/ja00166a070
CAS Web of Science® Google Scholar
10Complexes 6⋅3 H₂O and 4⋅1.5 H₂O were prepared by grinding phosphazenes with stoichiometric amounts of water.
Google Scholar
11
11aJ. Albertsson, S. C. Abrahams, Å. Kvick, Acta Crystallogr. Sect. B 1989, 45, 34;
10.1107/S0108768188010109
Web of Science® Google Scholar
11bS. C. Abrahams, J. L. Bernstein, Acta Crystallogr. Sect. B 1969, 25, 1233.
10.1107/S0567740869003876
CAS Web of Science® Google Scholar
12
12aC. H. Bates, W. B. White, R. Roy, Science 1962, 137, 993;
10.1126/science.137.3534.993
CAS PubMed Web of Science® Google Scholar
12bS. Desgreniers, Phys. Rev. B 1998, 58, 14102.
10.1103/PhysRevB.58.14102
CAS Web of Science® Google Scholar
13J. F. Bickley, R. Bonar-Law, G. T. Lawson, P. I. Richards, F. Rivals, A. Steiner, S. Zacchini, Dalton Trans. 2003, 1235.
10.1039/b212308h
CAS Web of Science® Google Scholar
14G. M. Sheldrick, SHELX-97, Universität Göttingen, 1997.
Google Scholar