Tetrakarbonil(4-tert-bütilpiridin)metal(0) Kompleks Bileşiklerinin Sentezi ve Spektroskopik Karakterizasyonu
Yıl 2020,
, 572 - 577, 31.01.2020
Özlem Ünlü
,
İzzet Amour Morkan
Öz
Hekzakarbonilmetal(0); M:Cr, Mo, W,
bileşikleri ile sübstitüye piridin (tert-bütilpiridin) arasında,
10 ºC de yapılan fotokimyasal tepkimeler, cis-tetrakarbonil(tert-bütilpiridin)metal(0)
bileşiklerini oluşturmaktadır. Sentezlenen bu organometalik bileşikler yüksek
vakum kullanılarak yeniden kristallendirme yöntemi ile saflaştırılır ve
yapıları FTIR-, 1H- ve 13C-NMR spektroskopileriyle
incelenir. Spektroskopik incelemeler sonucunda elde edilen veriler piridin
ligand halkasının sp2 hibritli azotundan zayıf şekilde bağladığını
ortaya koymaktadır. Ayrıca, piridin halkasının 4-konumu üzerindeki
sübstitüentinin boyutunun, piridin ile merkezi atomun koordinasyonunu
engellemediği gösterilmiştir.
Destekleyen Kurum
Türkiye Bilimsel ve Teknolojik Araştırma Kurumu ve ve Bolu Abant İzzet Baysal Üniversitesi Bilimsel Araştırma Projeleri
Proje Numarası
TBAG 2146 102T041, BAP 2007.03.03.268
Teşekkür
Bu çalışma Türkiye Bilimsel ve Teknolojik Araştırma Kurumu (TÜBITAK, TBAG-2146) ve Bolu Abant İzzet Baysal Üniversitesi Bilimsel Araştırma Projeleri (BAP 2007.03.03.268) tarafından desteklenmiştir.
Kaynakça
- [1] N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, 2. baskı, Oxford, İngiltere: Elsevier, 1997.
- [2] A.F. Hill, Organotransition Metal Chemistry, 1. Baskı, Cambridge, İngiltere: Royal Society of Chemistry, 2002.
- [3] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry : Principles Of Structure And Reactivity, 4. baskı, New York, ABD: HarperCollins College Publishers, 1993.
[4] T.E. Bitterwolf, "Organometallic photochemistry at the end of its first century" Journal of Organometallic Chemistry, c. 689, ss. 3939–3952, 2004.
- [5] Ş.Ö. Yaman, E. Esentürk, C. Kayran, A.M. Önal, "Spectroelectrochemical Investigation of Pentacarbonyl(pyrazine)metal(0) (Metal = Cr, Mo, W) Complexes of Group 6 Elements," Z. Naturforsch, c. 57, ss. 92–98, 2002.
- [6] R.H. Crabtree, The organometallic chemistry of the transition metals, John Wiley, Connecticut, ABD, 2005.
- [7] W. Strohmeier, "Photochemische Substitutionen an Metallcarbonylen und deren Derivaten," Angewandte Chemie c. 76, ss. 873–881, 1964.
- [8] I.W. Stolz, G.R. Dobson, R.K. Sheline, "Infrared Spectra and Structures of Metal Carbonyl Derivatives. III. Acetylene and Olefin Derivatives of Group VI Metal Carbonyls," Inorg. Chem. c. 2, ss. 1264–1267, 1963.
- [9] F.-W. Grevels, V. Skibbe, "Pentacarbonyl (η 2 -cis-cyclo-octene)chromium: photochemical synthesis of a useful Cr(CO)5 transfer reagent," Angewandte Chemie, c. 23, s. 11, ss. 681–683, 1984.
- [10] W. Gerhartz, F.-W. Grevels, W.E. Klotzbücher, E.A. Koerner Von Gustorf, R.N. Perutz, "Low-Temperature Matrix Photochemistry of (f/4-Diene)tetracarbonylchromium Complexes," Z. Naturforsch, s. 40, ss. 518-523, 1985.
- [11] C. Tuç, İ.A. Morkan, S. Özkar, "Synthesis and spectroscopic characterization of group 6 pentacarbonyl(4-substituted pyridine)metal(0) complexes," Transition Metal Chemistry, c. 32, ss. 727–731, 2007.
- [12] M.A. Weiner, A. Gin, M. Lattman, "Ultraviolet photoelectron spectra of 4-substituted pyridine-pentacarbonylchromium complexes," Inorganica Chimica Acta, c. 24, ss. 235–238, 1977.
- [13] J. Nasielski, A. Colas, "Quantum yield for photosubstitution of a co group in chromium hexacarbonyl by pyridine," Journal of Organometallic Chemistry, c. 101, ss. 215–219, 1975.
- [14] J. Nasielski, A. Colas, "The primary process in the photochemistry of Group 6B metal hexacarbonyls,", Inorganic Chemistry, c. 17, ss. 237–240, 1978.
- [15] R.J. Dennenberg, D.J. Darensbourg, "Infrared and kinetic studies of Group VI metal pentacarbonyl amine compounds," Inorganic Chemistry, c. 11, ss. 72–77, 1972.
- [16] M.J. Aroney, R.M. Clarkson, T.W. Hambley, R.K. Pierens, "A study of polarities, polarisabilities and infrared spectra of LM(CO)5 complexes (M ; Cr, Mo or W; L = trimethylamine, quinuclidine, pyridine, p-methyl- or p-t-butylpyridine) and of the X-ray crystal structure of quinuclidine-Cr(CO)5: Evidence for π-acceptor behaviour of coordinated pyridine," Journal of Organometallic Chemistry, c. 426, ss. 331–342, 1992.
- [17] H. Van Dam, G. Boxhoorn, D.J. Stufkens, A. Oskam, "π-backbonding in the metal-nitrogen bond in Cr(CO)5L type complexes," Inorganica Chimica Acta, c. 53, ss. 235-236, 1981.
- [18] R.M. Kolodziej, A.J. Lees, "Photophysics and photochemistry of a series of M(CO)5L complexes where M = Cr or Mo and L = pyridine or a substituted pyridine," Organometallics, c. 5, ss. 450–455.
- [19] B.S. Creaven, R.A. Howie, C. Long, "Pentacarbonyl(di-2-pyridylamine)tungsten(0)," Acta Crystallographica Section C Crystal Structure Communications, c. 56, ss. 182-183, 2000.
- [20] B.S. Creaven, R.A. Howie, C. Long, "Pentacarbonyl(4-phenylpyridine)tungsten(0) and pentacarbonyl(2-phenylpyridine)chromium(0)," Acta Crystallographica Section C Crystal Structure Communications, c. 57, ss. 385–387, 2001.
- [21] D.J. Darensbourg, B.J. Frost, D.L. Larkins, J.H. Reibenspies, "Organometallic Complexes of Uracil and Orotic Acid Derivatives: Coordination Mode, Structure, and Reactivity," European Journal of Inorganic Chemistry, c. 2000, ss. 2487–2495, 2000.
- [22] P.S. Braterman, Metal carbonyl spectra, Londra, İngiltere: Academic Press, 1975.
Synthesis and Spectroscopic Analysis of Tetracarbonyl(4-tert-butylpyridine)metal(0) Complexes
Yıl 2020,
, 572 - 577, 31.01.2020
Özlem Ünlü
,
İzzet Amour Morkan
Öz
The photolysis of
hexacarbonylmetal(0); M: Cr, Mo, W, complexes in the presence of a substituted
pyridine ligand (tert-butylpyridine) at
10 ºC yields the corresponding cis-tetracarbonyl(tert-butylpyridine)metal(0)
complexes. These synthesized organometallic complexes are purified under high
vacuum by recrystallization and their structures are investigated by using IR-,1H-
and 13C-NMR spectroscopies. Spectroscopic investigations reveal that
the pyridine ligand bonded the central atom weakly through the sp2
hybridized nitrogen atom of the ring. In addition to that the size of the
substituent does not hinder the coordination of the pyridine through the central
metal atom.
Proje Numarası
TBAG 2146 102T041, BAP 2007.03.03.268
Kaynakça
- [1] N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, 2. baskı, Oxford, İngiltere: Elsevier, 1997.
- [2] A.F. Hill, Organotransition Metal Chemistry, 1. Baskı, Cambridge, İngiltere: Royal Society of Chemistry, 2002.
- [3] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry : Principles Of Structure And Reactivity, 4. baskı, New York, ABD: HarperCollins College Publishers, 1993.
[4] T.E. Bitterwolf, "Organometallic photochemistry at the end of its first century" Journal of Organometallic Chemistry, c. 689, ss. 3939–3952, 2004.
- [5] Ş.Ö. Yaman, E. Esentürk, C. Kayran, A.M. Önal, "Spectroelectrochemical Investigation of Pentacarbonyl(pyrazine)metal(0) (Metal = Cr, Mo, W) Complexes of Group 6 Elements," Z. Naturforsch, c. 57, ss. 92–98, 2002.
- [6] R.H. Crabtree, The organometallic chemistry of the transition metals, John Wiley, Connecticut, ABD, 2005.
- [7] W. Strohmeier, "Photochemische Substitutionen an Metallcarbonylen und deren Derivaten," Angewandte Chemie c. 76, ss. 873–881, 1964.
- [8] I.W. Stolz, G.R. Dobson, R.K. Sheline, "Infrared Spectra and Structures of Metal Carbonyl Derivatives. III. Acetylene and Olefin Derivatives of Group VI Metal Carbonyls," Inorg. Chem. c. 2, ss. 1264–1267, 1963.
- [9] F.-W. Grevels, V. Skibbe, "Pentacarbonyl (η 2 -cis-cyclo-octene)chromium: photochemical synthesis of a useful Cr(CO)5 transfer reagent," Angewandte Chemie, c. 23, s. 11, ss. 681–683, 1984.
- [10] W. Gerhartz, F.-W. Grevels, W.E. Klotzbücher, E.A. Koerner Von Gustorf, R.N. Perutz, "Low-Temperature Matrix Photochemistry of (f/4-Diene)tetracarbonylchromium Complexes," Z. Naturforsch, s. 40, ss. 518-523, 1985.
- [11] C. Tuç, İ.A. Morkan, S. Özkar, "Synthesis and spectroscopic characterization of group 6 pentacarbonyl(4-substituted pyridine)metal(0) complexes," Transition Metal Chemistry, c. 32, ss. 727–731, 2007.
- [12] M.A. Weiner, A. Gin, M. Lattman, "Ultraviolet photoelectron spectra of 4-substituted pyridine-pentacarbonylchromium complexes," Inorganica Chimica Acta, c. 24, ss. 235–238, 1977.
- [13] J. Nasielski, A. Colas, "Quantum yield for photosubstitution of a co group in chromium hexacarbonyl by pyridine," Journal of Organometallic Chemistry, c. 101, ss. 215–219, 1975.
- [14] J. Nasielski, A. Colas, "The primary process in the photochemistry of Group 6B metal hexacarbonyls,", Inorganic Chemistry, c. 17, ss. 237–240, 1978.
- [15] R.J. Dennenberg, D.J. Darensbourg, "Infrared and kinetic studies of Group VI metal pentacarbonyl amine compounds," Inorganic Chemistry, c. 11, ss. 72–77, 1972.
- [16] M.J. Aroney, R.M. Clarkson, T.W. Hambley, R.K. Pierens, "A study of polarities, polarisabilities and infrared spectra of LM(CO)5 complexes (M ; Cr, Mo or W; L = trimethylamine, quinuclidine, pyridine, p-methyl- or p-t-butylpyridine) and of the X-ray crystal structure of quinuclidine-Cr(CO)5: Evidence for π-acceptor behaviour of coordinated pyridine," Journal of Organometallic Chemistry, c. 426, ss. 331–342, 1992.
- [17] H. Van Dam, G. Boxhoorn, D.J. Stufkens, A. Oskam, "π-backbonding in the metal-nitrogen bond in Cr(CO)5L type complexes," Inorganica Chimica Acta, c. 53, ss. 235-236, 1981.
- [18] R.M. Kolodziej, A.J. Lees, "Photophysics and photochemistry of a series of M(CO)5L complexes where M = Cr or Mo and L = pyridine or a substituted pyridine," Organometallics, c. 5, ss. 450–455.
- [19] B.S. Creaven, R.A. Howie, C. Long, "Pentacarbonyl(di-2-pyridylamine)tungsten(0)," Acta Crystallographica Section C Crystal Structure Communications, c. 56, ss. 182-183, 2000.
- [20] B.S. Creaven, R.A. Howie, C. Long, "Pentacarbonyl(4-phenylpyridine)tungsten(0) and pentacarbonyl(2-phenylpyridine)chromium(0)," Acta Crystallographica Section C Crystal Structure Communications, c. 57, ss. 385–387, 2001.
- [21] D.J. Darensbourg, B.J. Frost, D.L. Larkins, J.H. Reibenspies, "Organometallic Complexes of Uracil and Orotic Acid Derivatives: Coordination Mode, Structure, and Reactivity," European Journal of Inorganic Chemistry, c. 2000, ss. 2487–2495, 2000.
- [22] P.S. Braterman, Metal carbonyl spectra, Londra, İngiltere: Academic Press, 1975.