View PDF Version
 
DOI: 10.1039/A706028I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 637-646

Synthetic and single-crystal X-ray diffraction studies of CH2I2 and aryl iodide complexes of silver carboxylates and β-diketonates

(Note: The full text of this document is currently only available in the PDF Version )

John Powell, Michael J. Horvath, Alan Lough, Andrew Phillips and Jason Brunet

Abstract

The silver(I) iodocarbon complexes [{Ag2(O2CCF3)2(CH2I2)2}n] 1, [{Ag2(O2CCF3)2(1,2-I2C6H4)2}n] 2, [{Ag2(O2CCF3)2(1,4-I2C6H4)2}n] 3, [{Ag2(O2CCF3)2(IC6H5)}n] 4, [{Ag4(O2CCF3)4(H2O)2([hair space]p-IC6H4Me)2}n] 5, [{Ag2(O2CCF3)2(1,2-I2C6H4)}n] 6, [{Ag2(O2CCCl3)2(HO2CCCl3)(1,2-I2C6H4)}n] 7, [{Ag2(O2CCCl3)2(HO2CCCl3)(IC6H5)}n] 8, [{Ag4(hfacac)4([hair space]p-IC6H4Me)2] 10 (hfacac = 1,1,1,5,5,5-hexafluoroaceylacetonate) and [Ag4(hfacac)4(1,2-I2C6H4)3] 11 have been prepared and structurally characterized by single-crystal X-ray diffraction. The silver carboxylate complexes all contain carboxylate-bridged Ag2(carboxylate-O,O′)2 dimers (Ag–O 2.22–2.40 Å) with the intradimer Ag[hair space][hair space]· · ·[hair space][hair space]Ag distance varying in the range 2.9106(12) to 3.1527(14) Å which are the values observed for the alternating dimer units Ag2(O2CCF3)2(H2O)2 and Ag2(O2CCF3)2 observed in 5. In the complexes 1–3 the silver trifluoroacetate dimers are linked by I,I′-bridging I2R ligands with one ‘short’ Ag–I bond (2.94–3.05 Å) and one ‘long’ Ag–I bond (3.13–3.14 Å) per silver. In 4, 7 and 8 the Ag2(carboxylate-O,O′)2 dimers are extended into a chain polymer via Ag2O2 rings formed by co-ordination of each silver to an oxygen atom (Ag–O 2.33–2.51 Å) from an adjacent dimer. The 1,2-I2C6H4 forms an I,I′ bridge across the two silver atoms of the dimer unit in 7 [Ag–I 2.918(1) and 3.024(1) Å]. Complex 8 contains an acute angle bridging IC6H5 [Ag–I 2.927(2) and 2.970(2) Å, Ag–I–Ag 61.4(1)°], whilst in 4 the IC6H5 is semibridging [Ag–I 2.853(1) and 3.309(1) Å]. In complex 5 the two structurally different dimer units are bridged in a wide-angle fashion by p-IC6H4Me [Ag–I 2.9200(9) and 2.9333(8) Å, Ag–I–Ag 144.53(3)°]. Complex 6 contains eight-atom Ag2(O2CCF3-O,O′)2 rings linked to six-atom Ag2(O2CCF3-O,O′)(O2CCF3-O,O) rings which are interlinked to give an alternating 8646 ring chain polymer with I,I′-bridging 1,2-I2C6H4 across the two silvers of the six-atom rings [Ag–I 2.722(2) and 2.980(2) Å]. The hfacac complex 10 contains a tetranuclear unit in which the hfacac ligands both chelate and bridge whilst the p-iodotoluenes each bridge two silvers via η1-iodocarbon and η2-aryl co-ordination. Complex 11 is a tetranuclear unit in which three hfacac ligands both chelate and bridge whilst the fourth hfacac ligand bridges two silvers and forms a monodentate interaction with a third silver in a µ-O, η1-O′ mode. One 1,2-I2C6H4 ligand forms a monodentate interaction with a silver atom [Ag–I 3.064(3) Å] whilst the other two 1,2-I2C6H4 molecules function as highly unsymmetrical bidentate ligands [Ag–I 2.691(2), 3.350(2) and 2.719(2) and 3.228(2) Å]. The Ag–I–C bond angles vary from 85.9(4)° in 11 to 108.70(12)° in 3.

References

  1. D. M. Van Seggen, O. P. Anderson and S. H. Strauss, Inorg. Chem., 1992, 31, 2987 CrossRef CAS.
  2. M. R. Colsman, T. D. Newbound, L. J. Marshall, M. D. Noirot, M. M. Miller, G. P. Wulfsberg, J. S. Frye, O. P. Anderson and S. H. Strauss, J. Am. Chem. Soc., 1990, 112, 2349 CrossRef CAS.
  3. R. Scholl and W. Steinkopf, Chem. Ber., 1906, 39, 393 Search PubMed.
  4. J. Powell, M. Horvath and A. Lough, J. Chem. Soc., Chem. Commun., 1993, 733 RSC.
  5. J. Powell, M. Horvath and A. Lough, J. Chem. Soc., Dalton Trans., 1996, 1669 RSC.
  6. J. Powell, M. Horvath and A. Lough, J. Organomet. Chem., 1993, 456, C27 CrossRef CAS.
  7. R. G. Griffin, J. D. Ellett, M. Mehring, J. G. Bullit and J. S. Waugh, J. Chem. Phys., 1972, 57, 2147 CrossRef CAS.
  8. X.-M. Chen and T. C. W. Mak, J. Chem. Soc., Dalton Trans, 1991, 1219 RSC.
  9. C. Xu, T. S. Corbitt, M. J. Hampden-Smith, T. T. Kodas and E. N. Duesler, J. Chem. Soc., Dalton Trans., 1994, 2841 RSC.
  10. A. Bailey, T. S. Corbitt, M. J. Hampden-Smith, E. N. Duesler and T. T. Kodas, Polyhedron, 1993, 12, 1785 CrossRef CAS.
  11. H. C. Kang, A. W. Hanson, B. Eaton and V. Boekelheide, J. Am. Chem. Soc., 1985, 107, 1979 CrossRef CAS and refs. therein.
  12. F. Teixidor, J. A. Ayllón, C. Vinãs, J. Rius, C. Miravitlles and J. Casabó, J. Chem. Soc., Chem. Commun., 1992, 1279 RSC.
  13. R. J. Kulawiec and R. H. Crabtree, Coord. Chem. Rev., 1990, 99, 89 CrossRef CAS.
  14. G. M. Sheldrick, SHELXA in SHELXL 93, Program for Crystal Structure Refinement, University of Göttingen, 1993.
  15. G. M. Sheldrick, SHELXTL PC, Siemens Analytical X-ray Instruments, Madison, WI, 1990.
Click here to see how this site uses Cookies. View our privacy policy here.