VIBRATIONAL FREQUENCIES AND STRUCTURAL INVESTIGATION OF Pd(CN)4 2- ION

Year 2011, Issue: 026, 39 - 46, 15.12.2011

Cemal Parlak Hasan Bircan Metin Bilge Özgür Alver

Abstract

The normal mode frequencies and corresponding
vibrational assignments of Pd(CN)₄^2- ion have been
theoretically examined by means of standard quantum chemical techniques. All
normal modes have been assigned to one of six types of motion (CºN and Pd-C
stretching, Pd-CºN in plane and out of plane bending,   C-Pd-C in plane and out of plane bending)
utilizing the D_4h symmetry of Pd(CN)₄^2- ion. Calculations have been performed at HF, BLYP and B3LYP levels of theory using the Lanl2dz effective core basis set.
Infrared intensities and Raman activities of vibrational frequencies have also
been calculated. Theoretical results have been successfully compared against
available experimental data.

 

Keywords

Vibrational assignment, Normal mode frequency, Tetracyanopalladate (II) ion, DFT, Lanl2dz

Pd(CN)42- İYONUNUN TİTREŞİM FREKANSLARI VE YAPISAL İNCELEMESİ

Abstract

Pd(CN)₄^2- iyonunun normal mod
frekansları ve bunlara karşılık gelen titreşim işaretlemeleri standart kuantum
kimyasal teknikler yardımıyla kuramsal olarak incelenmektedir. Tüm normal
modlar Pd(CN)₄^2- iyonunun D_4h simetrisi
kullanılarak altı tür hareketten (CºN ve Pd-C gerilme, Pd-CºN düzlemde
ve düzlem dışı bükülme,     C-Pd-C düzlemde
ve düzlem dışı bükülme) birine işaretlenmektedir. Hesaplamalar etkin çekirdek baz
seti Lanl2dz kullanılarak HF, BLYP ve B3LYP yöntemleri ile yapılmaktadır. Titreşim
frekanslarının infrared şiddetleri ve Raman aktiviteleri de hesaplanmaktadır.
Kuramsal sonuçlar mevcut deneysel verilerle başarılı bir şekilde
karşılaştırılmaktadır. 

Keywords

Titreşim işaretlemesi, Normal mod frekansı, Tetrasiyanopaladyum (II) iyon, DFT, Lanl2dz

References

• [1] A.O. Legendre, A.E. Mauro, M.A.R. Oliveira, M.T.P. Gambardella, ‘‘A three-dimensional network constructed from the assembly of 1,3-diaminopropane-copper(II) and tetracyanopalladate(II) moieties’’, Inorg. Chem. Commun. 11: 896, (2008).
• [2] M. Munakata, J.C. Zhong, I. Ino, T. Kuroda-Sowa, M. Mackawa, Y. Sucnaga, N. Oiji, ‘‘1-D cyano-bridged heterometallic complexes consisting of 1,4,8,11-tetraazacyclotetradecanesilver (II) and tetracyanopalladium (II) or tetracyanoplatinum (II)’’, Inorg. Chim. Acta 317: 268, (2001).
• [3] R.L. Cordiner, M.P. Feroze, C.L. Fernandez, D.A. Jove, J.A.K. Howard, P.J. Low, ‘‘Trimetallic complexes featuring group 10 tetracyanometallate dianions as bridging ligands’’, Inorg. Chim. Acta 359: 3459, (2006).
• [4] S.C. Manna, J. Ribas, E. Zangrando, N.R. Chaudhuri, ‘‘Hetero-metallic frameworks of [Pd(CN)4]2− and Cu(II) with triamines: A rare example of a tetracyanometallate bridged 2D coordination polymer’’, Polyhedron 26: 3189, (2007).
• [5] H. Zhang, J. Cai, X.L. Feng, H.Y. Sang, J.Z. Liu, X.Y. Li, L.N. Ji, ‘‘Assembly chemistry of a cadmium (II) complex with cyanometalate anions [Fe(CN)5NO]2−, [Pd(CN)4]2− and [Pt(CN)6]2−’’, Polyhedron 21: 721, (2002).
• [6] J. Cernak, J. Skorsepa, K.A. Abboud, M.W. Meisel, M. Orendac, A. Orendacova, A. Feher, ‘‘Preparation, crystal structure and magnetic properties of Cu(en)2Pd(CN)4’’, Inorg. Chim. Acta 326: 3, (2001).
• [7] J. Cernak, J. Lipkowski, E. Cizmar, A. Orendacova, M. Orendac, A. Feher, M.W. Meisel, ‘‘Magneto-structural correlations in one-dimensional Ni(en)2Pd(CN)4: Magnetic properties and redetermination of the crystal structure at two temperatures’’, Solid State Sciences 5: 579, (2003).
• [8] M.L. Colin-Moreau, ‘‘Electronic spectra and structural properties of complex tetracyanides of platinum, palladium and nickel’’, Struct. Bond. 10: 167, (1972).
• [9] C. Muhle, J. Nuss, R.E. Dinnebier, M. Jansen, ‘‘Über Kaliumtetracyanoplatinat (II), Kaliumtetracyanopalladat (II) und deren Monohydrate’’, Z. Anorg. Allg. Chem. 630: 1462, (2004).
• [10] G.J. Kubas, and L.H. Jones, ‘‘Potential constants of the tetracyanide ions of nickel, palladium, and platinum’’, Inorg. Chem. 13: 2816, (1974).
• [11] C.E. Check, T.O. Faust, J.M. Bailey, B.J. Wright, T.M. Gilbert, L.S. Sunderlin, ‘‘Addition of polarization and diffuse functions to the Lanl2dz basis set for p-block elements’’, J. Phys. Chem. A 105: 8111, (2001).
• [12] I. Bytheway, M.W. Wong, ‘‘The prediction of vibrational frequencies of inorganic molecules using density functional theory’’, Chem. Phys. Lett. 282: 219, (1998).
• [13] Ö. Alver, C. Parlak, ‘‘DFT, FT-Raman, FT-IR, liquid and solid state NMR studies of 2,6-dimethoxyphenyl-boronic acid’’, Vibrational Spectroscopy, 54: 1, (2010).
• [14] C. Parlak, “Theoretical and experimental vibrational spectroscopic study of 4-(1-Pyrrolidinyl)piperidine”, J. Mol. Struct. 966: 1, (2010).
• [15] P.J. Hay and W.R. Wadt, ‘‘Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals’’, J. Chem. Phys. 82: 299, (1985).
• [16] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, ‘‘Gaussian 09 Revision A.01’’, (2009).
• [17] R.D. Dennington, T. A. Keith, J. M. Millam, GaussView 5.0.8, Gaussian Inc., (2008).
• [18] A. Vincent, ‘‘Molecular symmetry and group theory’’, Wiley, London, (1977).