<?xml version="1.0" encoding="ISO-8859-1"?><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">
<front>
<journal-meta>
<journal-id>0187-893X</journal-id>
<journal-title><![CDATA[Educación química]]></journal-title>
<abbrev-journal-title><![CDATA[Educ. quím]]></abbrev-journal-title>
<issn>0187-893X</issn>
<publisher>
<publisher-name><![CDATA[Universidad Nacional Autónoma de México, Facultad de Química]]></publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id>S0187-893X2015000400330</article-id>
<article-id pub-id-type="doi">10.1016/j.eq.2015.06.002</article-id>
<title-group>
<article-title xml:lang="en"><![CDATA[Spontaneously resolving chiral cis-[dinitrobis(ethylenediamine)cobalt]X complexes (X = Cl, Br) from the Alfred Werner collection of original samples at the University of Zurich - Alfred Werner's missed opportunity to become the 'Louis Pasteur' of coordination compounds]]></article-title>
<article-title xml:lang="es"><![CDATA[Resolución espontánea de complejos quirales cis-[dinitrobis(etilendiamina)cobalto]X (X = Cl, Br) de la colección de muestras originales de Alfred Werner en la Universidad de Zurich - Oportunidad perdida de Alfred Werner para convertirse en el "Louis Pasteur" de compuestos de coordinación]]></article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Blacque]]></surname>
<given-names><![CDATA[Olivier]]></given-names>
</name>
<xref ref-type="aff" rid="Aff"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname><![CDATA[Berke]]></surname>
<given-names><![CDATA[Heinz]]></given-names>
</name>
<xref ref-type="aff" rid="Aff"/>
</contrib>
</contrib-group>
<aff id="Af1">
<institution><![CDATA[,Switzerland Department of Chemistry ]]></institution>
<addr-line><![CDATA[Zurich ]]></addr-line>
<country>CH</country>
</aff>
<pub-date pub-type="pub">
<day>00</day>
<month>00</month>
<year>2015</year>
</pub-date>
<pub-date pub-type="epub">
<day>00</day>
<month>00</month>
<year>2015</year>
</pub-date>
<volume>26</volume>
<numero>4</numero>
<fpage>330</fpage>
<lpage>345</lpage>
<copyright-statement/>
<copyright-year/>
<self-uri xlink:href="http://www.scielo.org.mx/scielo.php?script=sci_arttext&amp;pid=S0187-893X2015000400330&amp;lng=en&amp;nrm=iso"></self-uri><self-uri xlink:href="http://www.scielo.org.mx/scielo.php?script=sci_abstract&amp;pid=S0187-893X2015000400330&amp;lng=en&amp;nrm=iso"></self-uri><self-uri xlink:href="http://www.scielo.org.mx/scielo.php?script=sci_pdf&amp;pid=S0187-893X2015000400330&amp;lng=en&amp;nrm=iso"></self-uri><abstract abstract-type="short" xml:lang="en"><p><![CDATA[17 original crystals of [&#923;-dinitrobis(ethylenediamine)cobalt]X complexes from the Alfred Werner collection of original samples of the University of Zurich were studied by single crystal X-ray diffraction revealing that the complexes with X = Cl, Br can undergo spontaneous chiral resolution upon crystallization. The main focus of this article was the chiral [&#923;- and &#916;-dinitrobis(ethylenediamine)cobalt]Cl complexes, which crystallize from racemic solution in the space group P 21 mainly as synthetical twins enriched in one enantiomer, but to a small extent also as pure enantiomorphs. The twinning effect was recognized and correctly described by PhD student Richard Hessen of the Alfred Werner group (PhD thesis 1914). Richard Hessen eventually resolved the [&#916;- and &#923;-dinitrobis(ethylenediamine)cobalt]Cl complex by the conglomerate salt resolution method. Based on the availability of the pure [&#916;- or &#923;-dinitrobis(ethylenediamine)cobalt]Cl complex, he carried out seeding experiments, which proved that the [&#916;- and &#923;-dinitrobis(ethylenediamine)cobalt]Cl complexes can be enriched to a great extent in one enantiomer by spontaneous chiral resolution. Already in the period of time from 1900 to 1904, various PhD students of Alfred Werner's group (Adolf Grün, Edith Humphrey, Ernst Zinggeler, Heinrich Schwarz, and Paul Larisch) prepared the [&#916;- or &#923;-dinitrobis(ethylenediamine)cobalt]Cl complex. Adolf Grün and Edith Humphrey have prepared enantiomerically enriched and rarely also enantiomorphic crystals of the [&#923;- or &#916;-dinitrobis(ethylenediamine)cobalt]Cl complex and could have separated crystals by manual crystal picking. Admittedly due to the crystal habits this would have been a difficult endeavour, but this 'Louis Pasteur method' was apparently not taken into consideration. Still in a cautiously sounding note one could state that Alfred Werner and his group had missed by this omission the opportunity for spontaneous chiral resolution of the [&#916;- and &#923;-dinitrobis(ethylenediamine)cobalt]Cl complexes in the period of time from 1900 to 1904. In addition, making this early chiral resolution story even more incredible, we found that Heinrich Schwarz and Paul Larisch applied in these early days of coordination chemistry the S-(D-,d-)camphorsulfonate anion to achieve the separation of the cis- and trans-isomers of the [dinitrobis(ethylenediamine)cobalt] complexes. They did not approach the potentially possible chiral resolution of the [cis-dinitrobis(ethylenediamine)cobalt]+ cation. But based on their synthetic procedure they did indeed accomplish chiral resolution of the cis-isomer and prepared eventually a series of the chiral [cis-,&#923;-dinitrobis(ethylenediamine)cobalt]X salts; however all this was in an unintentional manner.]]></p></abstract>
<abstract abstract-type="short" xml:lang="es"><p><![CDATA[Diecisiete cristales originales de los complejos [&#923;-dinitrobis(etilendiamina)cobalto]X, pertenecientes a la colección de muestras originales de Alfred Werner, de la Universidad de Zurich, fueron estudiados mediante difracción de rayos X de monocristal, encontrándose que los complejos con X = Cl, Br pueden resolver su quiralidad espontáneamente a través de la cristalización. El objetivo principal de este artículo fueron los complejos quirales [&#923;- y &#916;-dinitrobis(etilendiamina)cobalto]Cl los cuales cristalizan desde una solución racémica en el grupo espacial P 21 primordialmente como twins sintéticos enriquecidos en un enantiómero, y también en una pequeña medida como enantiomorfos puros. El efecto twinning fue reconocido y correctamente descrito por el estudiante de doctorado Richard Hessen (tesis doctoral en 1914) perteneciente al grupo de Alfred Wegner. Richard Hessen pudo eventualmente resolver el complejo [&#916;- y &#923;-dinitrobis(etilendiamina)cobalto]Cl mediante el método de resolución del conglomerado de sal basándose en la disponibilidad de complejo [&#916;- o &#923;-dinitrobis(etilendiamina)cobalto]Cl puro; llevó a cabo diversos experimentos de sembrado, los cuales concluyeron que los complejos [&#916;- o &#923;-dinitrobis(etilendiamina)cobalto]Cl pueden enriquecer en gran medida un enantiómero mediante resolución quiral espontánea. Ya en el periodo de 1900 a 1904 varios estudiantes de doctorado del grupo de Alfred Werner (Adolf Grün, Edith Humphrey, Ernst Zinggeler, Heinrich Schwarz, Paul Larisch) prepararon los complejos [&#916;- o &#923;-dinitrobis(etilendiamina)cobalto]Cl. Adolf Grün y Edith Humphrey prepararon cristales enriquecidos enantioméricamente y, extrañamente, a la vez cristales enantiomórficos de los complejos [&#916;- o &#923;-dinitrobis(etilendiamina)cobalto]Cl, los cristales pudieron ser separados manualmente. Es cierto, que debido al comportamiento de los cristales, esto debería haber sido un esfuerzo muy dificultoso, sin embargo este 'método de Louis Pasteur' aparentemente no fue tomado en consideración. Aun así, hablando con cautela, se podría decir que Alfred Werner y su grupo, mediante esta omisión, perdieron la oportunidad de lograr la resolución quiral espontánea de los complejos [&#916;- o &#923;-dinitrobis(etilendiamina)cobalto]Cl en el periodo de tiempo de 1900 a 1904. Además, haciendo la historia temprana de la resolución quiral aun más increíble, encontramos que Heinrich Schwarz y Paul Larisch aplicaron en los inicios de la química de coordinación el anión S-(D-,d-) sulfonato de alcanfor para conseguir la separación de los isómeros cis y trans de los complejos [dinitrobis(etilendiamina)cobalto]. Ellos no se acercaron a la potencialmente posible resolución quiral del catión [cis-dinitrobis(etilendiamina)cobalto]+. Pero basados en sus procedimientos sintéticos, efectivamente lograron la resolución quiral del isómero cis y prepararon, eventualmente una serie de sales quirales [cis-,&#923;-dinitrobis(etilendiamina)cobalto]X, sin embargo todo esto, de una forma casual.]]></p></abstract>
<kwd-group>
<kwd lng="es"><![CDATA[Alfred Wegner]]></kwd>
<kwd lng="es"><![CDATA[Compuestos de coordinación]]></kwd>
<kwd lng="es"><![CDATA[Quiralidad]]></kwd>
<kwd lng="es"><![CDATA[Resolución de conglomerado]]></kwd>
<kwd lng="es"><![CDATA[Resolución quiral espontánea]]></kwd>
<kwd lng="es"><![CDATA[Twinning sintético]]></kwd>
<kwd lng="es"><![CDATA[Sales de [dinitrobis(etilendiamina)cobalto]]]></kwd>
<kwd lng="en"><![CDATA[Alfred Werner]]></kwd>
<kwd lng="en"><![CDATA[Coordination compounds]]></kwd>
<kwd lng="en"><![CDATA[Chirality]]></kwd>
<kwd lng="en"><![CDATA[Conglomerate resolution]]></kwd>
<kwd lng="en"><![CDATA[Spontaneous chiral resolution]]></kwd>
<kwd lng="en"><![CDATA[Synthetical twinning]]></kwd>
<kwd lng="en"><![CDATA[[Dinitrobis(ethylenediamine)cobalt] salts]]></kwd>
</kwd-group>
</article-meta>
</front><back>
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