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<meta content="Astley, T." name="eprints.creators_name" />
<meta content="Canty, A.J." name="eprints.creators_name" />
<meta content="Hitchman, M.A." name="eprints.creators_name" />
<meta content="Rowbottom, G.L." name="eprints.creators_name" />
<meta content="Skelton, B.W." name="eprints.creators_name" />
<meta content="White, A.H." name="eprints.creators_name" />
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<meta content="Structural, Spectroscopic and Angular-overlap Studies of
the Nature of Metal-Ligand Bonding for Tripod Ligands" name="eprints.title" />
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<meta content="The metal(II) complexes [M((pz)2(py)CH}2][NO3]2 (M = Fe, Co, Ni, Cu or Zn), where (pz)2(py)CH is the unsymmetrical tripodal nitrogen-donor ligand bis(pyrazo1-1-yl)(pyridin-2-yl)methane, have been prepared and examined by single-crystal X-ray diffraction and single-crystal electronic
spectroscopy. The structural studies, and the application of the angular overlap model to the spectroscopic results, provide new information on the bonding characteristics of tripod ligands and a comparison of pyrazole and pyridine groups. The zinc complex crystallizes in both the monoclinic(P21/c) and triclinic (P1 bar) systems, the monoclinic complex being isomorphous with those of cobalt
and copper. The cations are centrosymmetric, but exhibit disorder in the orientation of the pyrazole and pyridine rings, except for the copper complex which exhibits a Jahn-Teller distortion involving two Cu-N(pz) bonds which are ca. 0.038 A longer than the other Cu-N distances. Except for the copper complex, the ligands form 'bite' angles N-M-N of 83.8(2)-86.9(2), resulting in a slight trigonal distortion from octahedral geometry. The tripod ligand produces a relatively strong ligand field, consistent with the rather short metal-nitrogen bond lengths in the complexes. The pyridine group is a slightly stronger sigma donor than the pyrazole groups, with both amines acting as weak pi donors." name="eprints.abstract" />
<meta content="1991" name="eprints.date" />
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<meta content="Journal of the Chemical Society, Dalton Transactions" name="eprints.publication" />
<meta content="8" name="eprints.volume" />
<meta content="1981-1990" name="eprints.pagerange" />
<meta content="10.1039/DT9910001981" name="eprints.id_number" />
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<meta content="1 See, for example, C. C. Tang, D. Davalian, P. Huang and R. Breslow,
J. Am. Chem. Soc., 1978,100,3918; R. S. Brown and J. Huguet, Can.
J. Chem., 1980, 58, 889.
2 See, for example, S. Trofimenko, Chem. Rev., 1972, 72, 497; Prog.
Znorg. Chem., 1986,34,115.
3 T. A. Hafeli and F. R. Keene, Aust. J. Chem., 1988,41,1379.
4 P. K. Byers, A. J. Canty, B. W. Skelton and A. H. White, J. Chem.
SOC., Chem. Commun., 1987, 1093; P. K. Byers, A. J. Canty, B. W.
Skelton and A. H. White, Organometallics, 1990,9, 826.
5 R. K. Boggess and D. A. Zatko, Znorg. Chem., 1976, 15, 626; R. K.
Boggess and D. A. Zatko, Inorg. Nucl. Chem. Lett., 1976,12,7.
6 J. Glerup, 0. Marnsted and C. E. Schaffer, Inorg. Chem., 1976, 15,
1399; 1980,19,2855; D. W. Smith, Znorg. Chem., 1978,17,3153.
7 P. K. Byers, A. J. Canty and R. T. Honeyman, J. Organomet. Chem.,
1990,385,417.
8 International Tables for X-Ray Crystallography, eds., J. A. Ibers and
W. C. Hamilton, Kynoch Press, Birmingham, 1974, vol. 4.
9 The XTAL System, Technical Report TR-1364, eds., S. R. Hall and
J. M. Stewart, Computer Science Center, University of Maryland,
1989.
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Sect. B, 1970, 26, 521; C. W. Reimann, A. D. Mighell and F. A.
Mauer, Acta Crystallogr., 1967, 23, 135; R. W. M. ten Hoedt, W. L.
Driessen and G. C. Verschoor, Acta Crystallogr., Sect. C, 1983, 39,
71.
G. J. Long and P. J. Clarke, Znorg. Chem., 1978,17,1394; F. Valach, P.
Sivy and N. Koren, Acta Crystallogr., Sect. C, 1984, 40, 957; D. J.
Hamm, J. Bordner and A. F. Schreiner, Znorg. Chim. Acta, 1973, 7,
637.
M. A. Hitchman, Transition Metal Chemistry (New York), 1985,9, 1.
F. Felix, J. Fergusen, H. U. Giidel and A. Ludi, Chem. Phys. Lett.,
1979,62, 153.
J. Van Houten and R. J. Watts, Inorg. Chem., 1978, 17, 3381.
T. Astley and M. A. Hitchman, unpublished work.
J. P. Jesson, S. Trofimenko and D. R. Eaton, J. Am. Chem. Soc.,
1967,89,3158.
M. A. Hitchman, Inorg. Chem., 1985,24,4762.
C. W. Reimann, J. Phys. Chem., 1970,74,561.
C. K. Jarrgensen, Absorption Spectra and Chemical Bonding,
Pergamon, Oxford, 1962, p. 124.
D. A. Cruse, J. E. Davies, M. Gerloch, J. H. Harding, D. Mackey
and R. F. McMeeking, CAMMAG, a Fortran Computing Package,
University of Cambridge, 1979.
A. Bencini, C. Benelli and D. Gatteschi, Coord. Chem. Rev., 1984,
60, 131; B. J. Kennedy, K. S. Murray, M. A. Hitchman and G. L.
Rowbottom, J. Chem. Soc., Dalton Trans., 1987,825.
R. G. McDonald and M. A. Hitchman, Inorg. Chem., 1990, 29,
3074.
A. D. Mighell, A. Santoro, E. Prince and C. W. Reimann, Acta
Crystallogr., Sect. B, 1975, 31,2479.
S. Minomura and H. G. Drickamer, J. Chem. Phys., 1961, 35, 903;
H. G. Drickamer, J. Chem. Phys., 1967,47,1880.
D. W. Smith, J. Chem. Phys., 1969, 50, 2784; M. Bermejo and L.
Pueyo, J. Chem. Phys., 1983,78,854.
R. G. McDonald, M. J. Riley and M. A. Hitchman, Znorg. Chem.,
1988, 27, 894; R. G. McDonald and M. A. Hitchman, Znorg. Chem.,
1989,28,3996.
D. M. L. Goodgame, M. A. Hitchman and B. Lippert, Inorg. Chem.,
1986,25,2191.
D. W. Smith, Inorg. Chim. Acta, 1977,22, 107.
L. G. Vanquickenborne and A. Ceulemans, Znorg. Chem., 1981,20,
796.
30 M. A. Hitchman and J. B. Bremner, Inorg. Chim. Acta, 1978, 27,
31 R. J. Deeth and M. Gerloch, Inorg. Chem., 1984,23,3853.
32 M. Gerloch, R. F. McMeeking and M. White, J. Chem. Soc., Dalton
Trans., 1976, 655; A. Bencini, C. Benelli, D. Gatteschi and C.
Zanchini, Inorg. Chem., 1980,19, 1301.
33 C. W. Reiman, A. D. Mighell and F. A. Mauer, Acta Crystallogr.,
1967, 23, 135; G. J. Long and P. J. Clarke, Inorg. Chem., 1978, 17,
1394.
L61.
34 A. J. Canty and C. V. Lee, Organometallics, 1982,1, 1063.
35 P. K. Byers and A. J. Canty, J. Chem. SOC., Chem. Commun., 1988,
639; D. G. Brown, P. K. Byers and A. J. Canty, Organometallics,
1990,9, 1231." name="eprints.referencetext" />
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<meta content="The metal(II) complexes [M((pz)2(py)CH}2][NO3]2 (M = Fe, Co, Ni, Cu or Zn), where (pz)2(py)CH is the unsymmetrical tripodal nitrogen-donor ligand bis(pyrazo1-1-yl)(pyridin-2-yl)methane, have been prepared and examined by single-crystal X-ray diffraction and single-crystal electronic
spectroscopy. The structural studies, and the application of the angular overlap model to the spectroscopic results, provide new information on the bonding characteristics of tripod ligands and a comparison of pyrazole and pyridine groups. The zinc complex crystallizes in both the monoclinic(P21/c) and triclinic (P1 bar) systems, the monoclinic complex being isomorphous with those of cobalt
and copper. The cations are centrosymmetric, but exhibit disorder in the orientation of the pyrazole and pyridine rings, except for the copper complex which exhibits a Jahn-Teller distortion involving two Cu-N(pz) bonds which are ca. 0.038 A longer than the other Cu-N distances. Except for the copper complex, the ligands form 'bite' angles N-M-N of 83.8(2)-86.9(2), resulting in a slight trigonal distortion from octahedral geometry. The tripod ligand produces a relatively strong ligand field, consistent with the rather short metal-nitrogen bond lengths in the complexes. The pyridine group is a slightly stronger sigma donor than the pyrazole groups, with both amines acting as weak pi donors." name="DC.description" />
<meta content="1991" name="DC.date" />
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<h1 class="ep_tm_pagetitle">Structural, Spectroscopic and Angular-overlap Studies of the Nature of Metal-Ligand Bonding for Tripod Ligands</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Astley, T.</span> and <span class="person_name">Canty, A.J.</span> and <span class="person_name">Hitchman, M.A.</span> and <span class="person_name">Rowbottom, G.L.</span> and <span class="person_name">Skelton, B.W.</span> and <span class="person_name">White, A.H.</span> (1991) <xhtml:em>Structural, Spectroscopic and Angular-overlap Studies of the Nature of Metal-Ligand Bonding for Tripod Ligands.</xhtml:em> Journal of the Chemical Society, Dalton Transactions, 8 . pp. 1981-1990. ISSN 1477-9226</p><p style="margin-bottom: 1em" class="not_ep_block"></p><table style="margin-bottom: 1em" class="not_ep_block"><tr><td valign="top" style="text-align:center"><a href="http://eprints.utas.edu.au/2853/1/Dalton1991_2C_1981.pdf"><img alt="[img]" src="http://eprints.utas.edu.au/style/images/fileicons/application_pdf.png" border="0" class="ep_doc_icon" /></a></td><td valign="top"><a href="http://eprints.utas.edu.au/2853/1/Dalton1991_2C_1981.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />1292Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input value="4075" name="docid" accept-charset="utf-8" type="hidden" /><div class=""><input value="Request a copy" name="_action_null" class="ep_form_action_button" onclick="return EPJS_button_pushed( '_action_null' )" type="submit" /> </div></form></td></tr></table><p style="margin-bottom: 1em" class="not_ep_block">Official URL: <a href="http://dx.doi.org/10.1039/DT9910001981">http://dx.doi.org/10.1039/DT9910001981</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">The metal(II) complexes [M((pz)2(py)CH}2][NO3]2 (M = Fe, Co, Ni, Cu or Zn), where (pz)2(py)CH is the unsymmetrical tripodal nitrogen-donor ligand bis(pyrazo1-1-yl)(pyridin-2-yl)methane, have been prepared and examined by single-crystal X-ray diffraction and single-crystal electronic
spectroscopy. The structural studies, and the application of the angular overlap model to the spectroscopic results, provide new information on the bonding characteristics of tripod ligands and a comparison of pyrazole and pyridine groups. The zinc complex crystallizes in both the monoclinic(P21/c) and triclinic (P1 bar) systems, the monoclinic complex being isomorphous with those of cobalt
and copper. The cations are centrosymmetric, but exhibit disorder in the orientation of the pyrazole and pyridine rings, except for the copper complex which exhibits a Jahn-Teller distortion involving two Cu-N(pz) bonds which are ca. 0.038 A longer than the other Cu-N distances. Except for the copper complex, the ligands form 'bite' angles N-M-N of 83.8(2)-86.9(2), resulting in a slight trigonal distortion from octahedral geometry. The tripod ligand produces a relatively strong ligand field, consistent with the rather short metal-nitrogen bond lengths in the complexes. The pyridine group is a slightly stronger sigma donor than the pyrazole groups, with both amines acting as weak pi donors.</p></div><table style="margin-bottom: 1em" border="0" cellpadding="3" class="not_ep_block"><tr><th valign="top" class="ep_row">Item Type:</th><td valign="top" class="ep_row">Article</td></tr><tr><th valign="top" class="ep_row">Subjects:</th><td valign="top" class="ep_row"><a href="http://eprints.utas.edu.au/view/subjects/250200.html">250000 Chemical Sciences > 250200 Inorganic Chemistry</a></td></tr><tr><th valign="top" class="ep_row">ID Code:</th><td valign="top" class="ep_row">2853</td></tr><tr><th valign="top" class="ep_row">Deposited By:</th><td valign="top" class="ep_row"><span class="ep_name_citation"><span class="person_name">Prof Allan J Canty</span></span></td></tr><tr><th valign="top" class="ep_row">Deposited On:</th><td valign="top" class="ep_row">14 Jan 2008 09:39</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">14 Jan 2008 09:39</td></tr><tr><th valign="top" class="ep_row">ePrint Statistics:</th><td valign="top" class="ep_row"><a target="ePrintStats" href="/es/index.php?action=show_detail_eprint;id=2853;">View statistics for this ePrint</a></td></tr></table><p align="right">Repository Staff Only: <a href="http://eprints.utas.edu.au/cgi/users/home?screen=EPrint::View&eprintid=2853">item control page</a></p>
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