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  • Acta Vol 53 p0090-0094

    Diunggah oleh

    Igor Vasiljevic
    5 tayangan5 halaman
    Acta Chemica Scandinavica

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    acta_vol_53_p0090-0094

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    Acta Chemica Scandinavica

    Hak Cipta:

    © All Rights Reserved
    Unduh sebagai PDF atau baca online dari Scribd
    Tandai sebagai konten tidak pantas
    5 tayangan5 halaman

    Acta Vol 53 p0090-0094

    Diunggah oleh

    Igor Vasiljevic
    Acta Chemica Scandinavica

    Hak Cipta:

    © All Rights Reserved
    Unduh sebagai PDF atau baca online dari Scribd
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    dari 5
    ee Preparation and Characterization of Lanthanide(IIl) Complexes with Polybenzimidazole Ligands. Crystal Structure of Bis[tris(N-methyl-1-benzimidazol-2-yl)- amine]lanthanumi(lII) Perchlorate Monoaceto! Solvate Liu Jiacheng,* Song Zhigang,* Wang Liufang,** Zhuang Jinzhong>* and Huang Xiaoying® “National Laboratory of Applied Organic Chemistry,Lanzhou University, Lanzhou 730000, P.R. China, "Coordination Chemistry Institute, Nanjing University, Nanjing 210093, P.R. China and “State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian 350002, P-R. China Li. J, Song. 2. L. Zhuang, J. and Huang, X.. 1999, Preparation snd. Characterization of Lanthanide(TII) Complexes. with Polybenzimidazole Ligands. Crystal Structure of Bis[tris(N-methyl-l-benzimidazol2-yl}amine)- lanthanum(Til) Perchlorate Monoacetonitrile Solvate. - Acta Chem. Scand. 33: ‘90-94, © Acta Chemica Seandinaviea 1999 Complexes with the composition [La(L")s|(C10,)s:mCHCN-nlL,0 and [Ln(L),1(C10,)-mCH,CN=nH,0 (La= La, Sm," Eu, Tm, Luisi methyl. -benzimidazol-2yl)amine, L*=iris(N-cthyl-[-benzimidazol-2-yl)amine; ‘m n=0 or I) have been characterized by infrared absorption spectroscopy (or the former) and elemental analysis, The X-ray erystal structure of the complex {(La(L!),}(C10,),°CHCN (Lat) has been determined. La-1 erystallizes in the ‘orthorhombic ‘space group P2,2,2, with a=12882(4), b=21,100(6), c= 22.706(6) and Z=4, The coordination geometey about the lanthanum( II) ion is best described as a slightly distorted triangulated dodecahedron comprising eight nitrogen atoms from two tetradentate igands (L") Lanthanides and their complexes are widely associated with their applications in chemistry, biochemistry, medi- cine and industry through their interesting properties (eg. Jow toxicity, luminescence and powerful paramagnetism) Although rare-earth metal cation complexes with anionic ligands containing oxygen as donor atoms have been the most studied,? more and more Ln"™ complexes derived from nitrogen donors. are being investigated and reported.”* In this work we report the syntheses and characterization of lanthanide(I1) complexes with the tripodal polybenzimidazole ligands wis(V-methyl-I-benz- imidazol-2y1)amine (L') and ris(N-ethyl-l-benzimidaz- ol-2y1)amine (1), having only nitrogens as coordinating centers and giving information on geometries with a coordination number of eight. fm Hort Is "To whom correspondence should be addressed. 90 © Acta Chemica Scandinavica 5311999) 90-98 Experimental Materials. The ligands tris(N-methyl-1-benzimidazol-2- yl)amine (L') and tris(N-ethyl--benzimidazol-2-yl}am- ine (L2) were synthesized by the methods described in Refs. 6 and 7. All other chemicals were commercially available and used without further purification. Caution: the perchlorate salts used in this study are potentially explosive and should be handled with care. Preparation of complexes. The complexes were all synthe- sized in a similar way. A typical example is as follows: {La(L'),|(C10,)y*CHCN (Lat), To L? (100mg, 0.22 mmol) dissolved in methanol (20 ml) was added La(C10,)3" H,0 (60 mg, 0.11 mmol) in methanol (5 ml) with stirring at room temperature, followed by precipita tion of the complex as a white power. After having been stirred for several hours the white precipitate was filtered off and recrystallized by vapour diffusion of diethylether into a filtered acetonitrile solution of the complex. ‘The cther complexes _[Ln(L),l(C10,)s*mCH CN -nl,0 (LaLa, Sm, Eu, Tm; L=L', L%m,n=0 or 1) were Table 1. Analytical data for the complexes. LANTHANIDE (it COMPLEXES WITH POLYBENZIMIDAZOLE LIGANDS Found (%) Caloulated (%) Complex c x N c 4 N Lat [LalLiz {C1045 -CH3CN 48.68 413 15.04 48.83 417 15.25 La-2 [LatL*gIC1O4)5 CH3CN HzO 50.08 amr 1405 50.33 434 1420 ‘Smet [SmiL'}g(ClOg}9: CHaCN 20 an 416 1497 4781 423 1493 ‘Sm-2 [Smil“ls]ClO¢IyCHgCN -H,0 49.65 451 1412 49.94 4.80 1409 Eu (Evil, {C104}, CHyCN-H.0 47.66 402 16.10 41.75 422 1492 £u2 (Evil) (C104), CHyCN HO 49.68 453, 1428 49.89 479 14.08 Tred [Trig HIC1O4)y-CHSCN 47.90 402 15.18 47.79 408, 1493 Tm2 mi, HCIO\}5 4951 459 1352 49.68 458, 1352 obtained by a similar procedure. Analytical data for the isolated complexes are shown in Table 1. Measurements. Microanalyses (C, H, N) were performed on a Carblo-Erba 1106 elemental analyzer. The IR spectra were recorded on a Nicolet-170SX FT-IR spec- trophotometer as KBr dises in the range 4000-200 em. X-Ray crystallographic data collection and structure deter- ‘mination. The single erystals of complex Lal were obtained by slow vapour diffusion of ether into aceto- nitrile solution of the complex. The data were collected on a Enraf-Nonius CADS diffractometer by the 0/20 scan mode with scan width 0.65 +0.35 tan 8, and a scan rate less than 5.49° min“, using graphite monochrom- ated Mo-Ka (2=0.71073 A) radiation. Details of the data collection and processing are given in Table 2. Data were corrected for Lorentz and polarization effects. An absorption correction was applied using Y-scan data. ‘The structure was solved by the heavy-atom method, followed by difference Fourier techniques. Refinement was carried out by fullmatrix least-squares. All the Table 2. Crystallographic data for [Lal."),\CIOq)y CCN. Empirial formula Layee NCO Formula weight sara Temperature) 296 Crystal system Orthorhombie Space group 2,2,2, (No. 19) aA 12.882(4) biA 21.10016), ° 2270846) Volume/A® 617206) Zz 4 Density (calculated /Mg m: 1.48 ‘Absorption coefficient/em"* asa +F(000) 2808 Crystal size/mm 055x025 030 index range Ocha 15; —25oU)) 4312 mE Fol [Fel ElFol 0.060 Ry=(EW Foi —|FolFEWIFaRY® 0.065 Lrgest diference peak and 1.20 and —1.13, holeje A hhydrogen atoms were generated geometrically, but not refined, The final R-value was 0.060, and the R,-value was 0,065 with w= 1/o(F). Atomic scattering factors were taken from Ref. 9. All calculations were performed on a MICRO VAX 3100 computer using the TEXSAN program package. Atomic coordinates of non-hydrogen atoms are listed in Table 3, and selected bond lengths and angles in Table 4, Structure factors, thermal parameters, coordinates of hydrogen atoms and least-squares planes are available from the authors as supplementary material, Results and discussion Deseription ofthe structure. The structure of the complex {La(L"),(C10,),*CH3CN consists of a (La(L'),* cation, three non-coordinated perchlorate counter-anions and one acetonitrile solvent molecule. A perspective view of the [La(L')s}** cation, with the atom numbering scheme, is shown in Fig, 1, while the coordination poly- hedron’ is shown in Fig.2. In the complex cation {[La(L'),)**, eight nitrogen atoms originating from two L! ligands form a distorted dodecahedron around the lanthanum atom. Its interesting to see that this complex presents two kinds of La-N bond distances. The longer bond lengths are 2,73(1) and 2.77(1) A for La-NI and La-N8, respectively, which nitrogen atoms are from the tertiary amine. The shorter bond lengths range from 2.54(1) to 2.58(1) A between the center La atom and N’ atoms from benzimidazole. The former values agree well with those observed in related systems such as La(OAr}s(NHy)g (Ar=2,6-PryCgHy) (La-N= 2.748-2.84 A)" and _(La(EDTA)(H,O)]”_(La-N 2.755 A).*" The latter is slightly shorter than those found in the complex (LaFe(L?),)°* {where L’=2-(6-(i- cthylcarbamoy!)pytidin-2-y1]-1,1'-dimethyl-2-(5-meth- ylpyridin-2- yl) 5,5’-methylenebis( 1H -benzimidazole)} (La-N=2.68(2) A)" As shown above, the La-N- (benzimidazole) bond lengths are significantly shorter than the La-N(amine) bond lengths, due in part to the greater r-bonding ability of benzimidazole pendants compared to alkylamines of only o-

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