Trivacant Heteropolytungstate Derivatives: 3:1Rational Syntheses, Characterization, Two-dimensional183w Nmr, and Properties of P2w18m4(h2o)2o681()- Andp4w3om4(h2o)2o11216-(m = Co, Cu, Zn)

Inorganic Chemistry

Volumn 26, Issue 23, 1987, Pages 3886-3896

  Finke, Richard G ^c   Droege, Michael W ^a   Domaille, Peter J ^b  

^a UNIVERSITY OF OREGON   (United States)

^b DUPONT COMPANY   (United States)

^c NONE

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0038969505     PISSN: 00201669     EISSN: 1520510X     Source Type: Journal    
DOI: 10.1021/ic00270a014     Document Type: Article

References (27)

1. Part 1: Finke, R. G.; Droege, M.; Hutchinson, J. R.; Gansow, O. J. Am. Chem. Soc. 1981, 103, 1587–1589. (b) Part 2: Finke, R. G.; Droege, M. W. Inorg. Chem. 1983, 22, 1006–1008. (c) For part 1 of our work on “Trisubstituted Heteropolyanions as Soluble Metal Oxide Analogues”, see: Finke, R. G.; Droege, M. W. J. Am. Chem. Soc. 1984, 106, 7274–7277. For part 2 see: Finke, R. G.; Rapko, B. M.; Domaille, P. J. Organometallics 1986, 5, 175. For part 3 see: Finke, R. G.; Rapko, B. M.; Saxton, R. J.; Domaille, P. J. J. Am. Chem. Soc. 1986, 108, 2947. For part 4 see: Edlund, D. J.; Finke, R. G., submitted for publication in Organometallics.
2. (a) Weakley, T. J. R.; Evans, H. T., Jr.; Showell, J. S.; Tourne, G. F.; Tourne, C. M. J. Chem. Soc., Chem. Commun. 1973, 139-140. Although a yield was not reported, repeating their synthesis provided 3.1g (29%) of this product along with 1.3 g of a blue insoluble byproduct.18 A deep rose-pink crystalline byproduct from this synthesis has been identified by a single-crystal X-ray diffraction analysis26 as P5Co9W270119H17l6_. (b) Professor Weakley has kindly provided us with a preprint of a follow-up full paper concerning this work: Evans, H. T., Jr.; Tourne, C. M.; Tourne, G. F.; Weakley, T. J. R. J. Chem. Soc., Dalton Trans. 1986, 2699. Described therein are the full details of their syntheses and of the original38 P2WIgCu4(OH2)2O6810 and now As2W,8Zn4(OH2)2O6810-X-ray diffraction structural analyses and the 183W NMR spectrum of P2W18Zn4(0H2)2068ll>(see also Table I herein
3. (a) we chose to try to mimic zno initially because zno is one of the best characterized examples among oxides as far as surface intermediates and reaction mechanisms are concerned48 (in large part due to the good ir properties of zno) and because the (zno)3 zinc oxide “minisurface” in “pw9(zn0)30349” closely resembles the 0001 or polar plane of zno.48 our focus on trisubstituted heteropolyanions like siw9m3o40*_ is derived in part from the fact that such a trisubstituted heteropolyanion offers the largest possible planar m^ot, (e.g. zn303) minisurface on the keggin, xw|2o40, anion. other design features include a high surface charge density, the possibility of a- vs b-type xwjmjo* comparisons, high (c3) symmetry simplifying spectroscopic properties, the 183w, x = 31p, 29si, and m = 51v nmr handles, and the possibility of the comparative series of siw9m3o40* and p2w15m304cr for m = v5+, nb5+, ta5+ and ti4+, zr4+, hf*+. for further details see ref lc. (b) John, C. S. in catalysis-, Kemball, G., dowden, d. a., eds.; the chemical society: london, 1980; vol. 3, pp 169, 187. (c) gay, r. r.; nodine, m. h.; henrich, v. e.; zeiger, h. j.; solomon, e. i. j. am. chem. soc. 1980, 102, 6752. see figure 1 therein, (d) the high anionic charge, the large size of zn2+ vs the size of the lacunary hole in pw90 349-, and the apparent high stability of p2wlgzn4(h20)206810- are factors that appear to mitigate against the, as yet unknown, pw9(zn0)30349” (or pw9(zn0h2)30 379), although siw9(cooh2)30 371' has been reported in a preliminary communication. 5
4. Katsoulis, D. E.; Pope, M. T. J. Am. chem. soc. 1984, 106, 2737.
5. weakley, t. j. r.; evans, h. t., jr.; showell, j. s.; tourne, g. f.; tourne, c. m. j. chem. soc., chem. commun. 1973, 139–140. al-
6. contain, r.; ciabrini, j. p. j. inorg. nucl. chem. 1981, 43, 1525. (b) contant, r.; ciabrini, j. p. j. chem. res., miniprint 1977, 2601; j. chem. res., synop. 1977, 222. (c) acerete, r.; hammer, c. f.; baker, l. c. w. inorg. chem, 1984, 23, 1478.
7. lefebvre, j.; chauveau, f.; doppelt, p.; brevard, c. j. am. chem. soc. 1981, 103,4589. (b) brevard, c.; schimpf, r.; tourne, g.; tourne, c. m. j. am. chem. soc. 1983, 105, 7059. (c) domaille, p. j.; knoth, w. h. inorg. chem. 1983, 22, 818.
8. massart, r.; content, r.; fruchart, j. m.; ciabrini, j. p.; fournier, m. inorg. chem. 1977,16, 2916–2921. (b) a vs b isomers (see figure
9. knoth, w. h.; domaille, p. j.; farlee, r. d. organometallics 1985, 4, 62–68.
10. massart, r.; contant, r.; fruchart, j. m.; ciabrini, j. p.; fournier, m. inorg. chem. 1977, 16, 2916–2921.
11. wu, h. j. biol. chem. 1920, 43, 189–220. (b) acerete, r.; hammer, c. f.; baker, l. c. w. j. am. chem. soc. 1979, 101, 267.
12. rocchiccioli-deltcheff, c.; thouvenot, r.; franck, r. spectrochim. acta, 1976, 32a, 587–597.
13. knoth, w. h.; domaille, p. j.; harlow, r. l. inorg. chem. 1986, 25, 1577. this work reports novel complexes from a-type pw9 such as
14. Acerete, R.; Hammer, C. F.; Baker, L. C. W. J. Am. chem. soc. 1979, 101, 267–269.
15. domaille, p. j. j. am. chem. soc. 1984, 106, 7677–7687.
16. mareci, t. h.; freeman, r. j. magn. reson. 1982, 48, 158–163.
17. rocchiccioli-deltcheff, c.; thouvenot, r. j. chem. res., synop. 1977, 46-47; j. chem. res., miniprint 544–571.
18. cotton, f. a.; wilkinson, g. advanced inorganic chemistry, 4th ed.; wiley-interscience: new york, 1980; pp 678–682.
19. harmalker, s. p.; leparulo, m. a.; pope, m. t. j. am. chem. soc. 1983, 105, 4286–4292.
20. acerete, r. ph.d. dissertation, georgetown university, 1981.
21. Weakley, T. J. R. J. Chem. Soc., chem. commun. 1984, 1406.
22. knoth, w. h.; harlow, r. l. j. am. chem. soc. 1981, 103, 1865. (b) 1,4-pv2w1o405_has been described: domaille, p. j.; watunya, g. inorg. chem. 1986, 25, 1239. (c) domaille, p. j.; harlow, r. l. j. am. chem. soc. 1986. 108. 2108.
23. one of the most massive, discrete heteropolyanions reported to date28b,c is mn+as4w40ol40n-28(b) leyrie, m.; herve, g. nouv. j. chim. 1978, 2, 233. (c) robert, f.; leyrie, m.; herve, g.; teze, a.; jeannin, y. inorg. chem. 1980, 19, 1746.
24. see ref 3–7 in: finke, r. g.; droege, m. w.; cook, j. c.; suslick, k. s. j.,am. chem. soc. 1984, 106, 5750–5751.
25. See, However: Evans, H. T., Jr.; Pope, M. T. Inorg. chem. 1984, 23, 501.
26. suslick, k. s.; cook, j. c.; rapko, b. m.; droege, m. w.; finke, r. g. inorg. chem. 1986, 25, 241.
27. corbridge, d. e. c. the structural chemistry of phosphorus; elsevier: amsterdam, 1974; p 467.