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Master's Dissertation
DOI
10.11606/D.54.1992.tde-22052009-115345
Document
Author
Full name
Marcos Roberto de Mattos Fontes
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 1992
Supervisor
Committee
Oliva, Glaucius (President)
Craievich, Aldo Felix
Torriani, Iris C Linares de
Title in Portuguese
Introdução aos métodos de determinação de estruturas cristalinas por difração de raios-X: complexos de Rutênio.
Keywords in Portuguese
Complexos de rutênio
Cristalografia
Difração de raios-X
Abstract in Portuguese
Esta dissertação consiste de duas partes: Parte I: Descrição teórica suscinta dos fundamentos da cristalografia de raios-X. Parte II: Resolução de quatro estruturas cristalinas, três complexos de rutênio (capítulos V, VI, VII) e um ligante comumente encontrado em complexos de rutênio, o C28H28O2P2. As estruturas resolvidas foram: 1) C28H28O2P2, Mr= 458.48, triclínico, PI a= 5.826(1), b= 8.862(1), c= 12.517(2)Å, α= 100.29(1), β= 102.67(1), Υ= 104.22(1)°, V= 592.5(3)Å3, Z=1, Dx=1.285g.cm-3, λ(MοKα)=0,71073Å, μ= 2.00cm-1, F(000)=242, T=296K, Rint=0.01, R=0.031, Rw=0.030 para 1390 reflexões independentes observadas [I> 3 ο (I)]. Os átomos P estão a 0.126(1)Å do plano formado pelo grupo (CH2)4-. Os anéis fenil são planares dentro da margem de erro experimental. Os átomos P têm uma configuração tetraédrica distorcida. 2) PyH[RuCl4(CO)Py], Mr=430.11, monoclínico, P21/n, a= 7.821(1), b= 10.337(3), c= 19.763(3)Å, β=93.07(1)°, V= 1595.5(5)Å3, Z=4, Dx=1.791g.cm-3, λ(MοKα)=0,71073Å, μ= 14.86cm-1, F(000)=843.9, T=296K, Rint=0.03, R=0.062, Rw=0.063 para 1478 reflexões independentes observadas [I> 3ο (I)]. A estrutura é composta essencialmente por dois planos perpendiculares entre si; um formado pelos quatro átomos de cloro (com ângulo de aproximadamente 90° entre si), o outro pelos grupos Py e carbonila e o átomo de Ru na intersecção destes. O complexo tem carga líquida negativa, sendo necessário a presença do grupo PyH (com carga líquida positiva), para a estabilização do cristal. 3) PyH(RuCl4Py2), Mr= 481.20, monoclínico, P21/n, a= 8.080(7), b= 22.503(7), c= 10.125(6)Å, β= 93.19(6)°, V= 1838(2)Å3, Z=4, Dx= 1.739g.cm-3, λ(MοKα)=0,71073Å, μ= 13.06cm-1, F(000)=959.9, T=296K, Rint=0.03, R=0.038, Rw=0.039 para 1553 reflexões independentes observadas [I> 3ο (I)]. Esta estrutura é bastante similar com a 2) descrita acima, ou seja, é composta essencialmente por dois planos perpendiculares entre si; um formado pelos quatro átomos de cloro (com ângulo de aproximadamente 90° entre si), o outro pelos dois grupos Py e o átomo de Ru na intersecção destes. Pelo mesmo argumento usado acima, há um grupo PyH (com carga líquida positiva) no cristal. 4) [RuCl2(MeIm)2(CH3OH)(CO)], Mr= 396.24, triclínico, PI, a= 8.609(3), b= 8.060(3), c= 10.581(4)Å, α= 77.78(3), β= 88.43(3), Υ= 66.88(3)°, V= 740.4(5)Å3, Z=2, Dx= 1.777g.cm-3, λ(MοKα)=0,71073Å, μ= 12.80cm-1, F(000)=386, T=296K, Rint=0.004, R=0.025, Rw=0.027 para 2489 reflexões independentes observadas [I> 3ο (I)]. As distâncias e ângulos médios das ligações dos quatro complexos aqui descritos são comparados entre si e com mais quatro complexos no capítulo VII.
Title in English
Introduction to crystal structure determination methods by X-ray diffraction: ruthenium complexes.
Keywords in English
Crystallography
Ruthenium complexes
X-ray diffraction
Abstract in English
This work consists of two parts: Part I: A brief theoretical description of the basic principles of X-ray crystallography. Part II: Resolution of the four crystal structures; three ruthenium compounds (chapter V, VI, VII) and a ligand commonly found in ruthenium complexes, C28H28O2P2. The structures resolved were: 1) C28H28O2P2, Mr= 458.48, triclinic, PI a= 5.826(1), b= 8.862(1), c= 12.517(2)Å, α= 100.29(1), β= 102.67(1), Υ= 104.22(1)°, V= 592.5(3)Å3, Z=1, Dx=1.285g.cm-3, λ(MοKα)=0,71073Å, μ= 2.00cm-1, F(000)=242, T=296K, final R=0.031 for 1390 independent observed reflections. The P atoms 0.126(1)Å away from plane formed by (CH2)4-. Both phenyl rings are planar to within experimental accuracy. The P atom has a distorced tetrahedral configuration. 2) PyH[RuCl4(CO)Py], Mr=430.11, monoclinic, P21/n, a= 7.821(1), b= 10.337(3), c= 19.763(3)Å, β=93.07(1)°, V= 1595.5(5)Å3, Z=4, Dx=1.791g.cm-3, λ(MοKα)=0,71073Å, μ= 14.86cm-1, F(000)=843.9, T=296K, Rint=0.03, final R=0.062, Rw=0.063 for 1478 independent observed reflections [I> 3ο (I)]. The structure is essentially composed of two perpendicular planes; one consisting of four chlorine atoms (in a square-planar arrangement), and a second plane composed of Py and carbonyl groups, with the ruthenium atom at intersection of them. The molecules have a net negative charge and the presence of the PyH group (with net positive charge), is necessary for crystal stabilization. 3) PyH(RuCl4Py2), Mr= 481.20, monoclinic, P21/n, a= 8.080(7), b= 22.503(7), c= 10.125(6)Å, β= 93.19(6)°, V= 1838(2)Å3, Z=4, Dx= 1.739g.cm-3, λ(MοKα)=0,71073Å, μ= 13.06cm-1, F(000)=959.9, T=296K, Rint=0.03, final R=0.038, Rw=0.039 for 1553 independent observed reflections [I> 3ο (I)]. This structures is very similar to that described in 2) above, being essentially composed of two perpendicular planes; one composed of four chlorine atoms (in a square-planar arrangement), and the other composed of two Py groups, with the ruthenium atom at the intersection of them. For the reason given above, there is one PyH group (with positive liquid charge) in the crystal. 4) [RuCl2(MeIm)2(CH3OH)(CO)], Mr= 396.24, triclinic, PI, a= 8.609(3), b= 8.060(3), c= 10.581(4)Å, α= 77.78(3), β= 88.43(3), Υ= 66.88(3)°, V= 740.4(5)Å3, Z=2, Dx= 1.777g.cm-3, λ(MοKα)=0,71073Å, μ= 12.80cm-1, F(000)=386, T=296K, Rint=0.004, final R=0.025, Rw=0.027 for 2489 independent observed reflections [I> 3ο (I)]. In chapter VII, the average inter-atomic distances and angles for the four compounds are compare one with another and with four previously determinate structures.
 
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Publishing Date
2009-05-26
 
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