Stereospecific Influences in Metal Complexes Containing Optically Active Ligands. Part I. Some of the Optical Isomers of Tris-(propylenediamine)-cobalt(III) Ion

Dwyer, Francis Patrick John; Garvan, Francis L.; Shulman, A.

doi:10.1021/ja01511a009

Cited by 108 publications

(24 citation statements)

References 1 publication

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“…Comparison of the structure of Mo2(02CCF3)4(py)2 with the previous results for Mo2-(02CCF3)416 provides a quantitative measure of the decrease in Mo-Mo bond strength upon coordination of pyridine as an axial donor. The 2.129 (2) A Mo-Mo bond length in the adduct is 0.039 (6) A greater than the value of 2.090 (4) Á obtained for the parent compound. The difference is statistically significant but rather small from a chemical viewpoint.…”

contrasting

confidence: 56%

Conformations of cyclic compounds in solution. V. Nuclear magnetic resonance study of the conformational preferences of some substituted ditertiary arsine chelate complexes of chromium carbonyl

Cullen¹,

Hall²,

Ward³

1972

J. Am. Chem. Soc.

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L may be. That is, the intrinsically strong Mo-Mo bond necessitates an intrinsically weak Mo-L bond. This "metal-metal trans effect" operates to some extent in the other dinuclear carboxylates. Thus, in Cr2-(0Ac)4(H20)2s and Cr30(0Ac)6(H20)3+,28 the average Cr-OAc distances of 2.018 (2) and 1.98 (1) A are comparable to each other and to the Cr-OH2 distance in the trimer, 2.02 (1) A, but all are significantly shorter than the Cr-OH2 distance in the dimer, 2.272 (3) A. In the dimer, the water molecule is trans to the Cr-Cr bond; in the trimer, to the Cr-0 bond. Again, the Rh-OH2 distance of 2.310 (3) A in Rh2(OAc)4(H20)2 is substantially greater than the average Rh-OAc distance of 2.039 (2) A. Nowhere is the trans effect more dramatically illustrated than in the molybdenum system, however; therefore, Mo(II) appears to have an intrinsically greater metal-metal bonding tendency in the carboxylate framework than do Cr(II) and Rh(II). This has long been suggested from theoretical considerations and the available X-ray data,7 but never so conclusively demonstrated. One expects, then, that if good crystals of unsolvated M2(02CCF3)4, M = Cr, Rh, could be obtained, which may not be possible, the Cr-Cr and Rh-Rh distances would definitely be longer than the Mo-Mo distance in Mo2(02CCF3)4, allowing for differences in covalent radii. Moreover, if crystalline M2(02CCF3)4(py)2, M = Cr, Rh, could be obtained, which should be possible, the metal-nitrogen distances should definitely be shorter than in Mo2-(02CCF3)4(py)2, again allowing for differences in covalent radii. The lengths found for metal-to-axial ligand bonds in the carboxylates thus provide valuable information about the implicit tendencies of the metals toward mutual attraction.

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contrasting

confidence: 56%

Conformations of cyclic compounds in solution. V. Nuclear magnetic resonance study of the conformational preferences of some substituted ditertiary arsine chelate complexes of chromium carbonyl

Cullen¹,

Hall²,

Ward³

1972

J. Am. Chem. Soc.

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“…It was cited a few times (slide 20 [1] ) in the period after 1945 until 1980 by the Australian school of Dwyer and Sargeson. [16,17] But after 1994, the number of citations of this classical publication has risen steadily again.…”

Section: The Development Of Stereochemistry Of Coordination Compoundsmentioning

confidence: 99%

Stereochemistry of Coordination Compounds. From Alfred Werner to the 21st Century

Zelewsky

2014

Chimia

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As a contribution to the scientific symposium, November 22nd, 2013, commemorating the Nobel Prize awarded to Alfred Werner in 1913, a presentation of the development of stereochemistry of coordination compounds during the past 120 years was given. Stereochemistry was fundamental to Werner's theory of coordination compounds. After Werner's death in 1919, stereochemistry in this field did not progress much further for almost 20 years, but then developed continuously. It was realized that stereochemical features of elements showing coordination numbers larger than four are responsible for an almost unlimited number of stereochemical possibilities, thus opening a molecular world of new structures. In the beginning of the 21st century, interest in the field rose again considerably, mainly due to the potential of stereoselective catalysis, and the self-assembly of supramolecular structures. An end of these developments is not in sight. Here an abbreviated version of the lecture is given. A PowerPoint(®) file, or a video of the presentation, can be downloaded.

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“…Schema 3 ] 3 quantitativ untersucht und eine Gleichgewichtskonstante von 5.75 bestimmt. [24] Eine ebenfalls klassische Serie von Versuchen zur Stereochemie wurde 1928 von Jaeger und Blumendal [25] Auch die b-Ketoenolate von Camphen hatten massgeblichen Anteil an der Entwicklung der anorganischen asymmetrischen Synthese. Camphen ist leicht in enantiomerenreiner Form zugänglich, und seine einfache Umwandlung in die Hydroxymethylenform L2 a wurde bereits 1894 beschrieben.…”

Section: Chiralität In Der Koordinationschemieunclassified

Prädeterminierte Chiralität an Metallzentren

1999

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Die asymmetrische Synthese in der Koordinationschemie wurde bereits 1920 durch Smirnoff klar beschrieben, aber anders als in der Organischen Chemie wurde die Möglichkeit der asymmetrischen Synthese in der Koordinationschemie über Jahrzehnte kaum genutzt. In jüngster Zeit hat das Interesse an Chiralität in der Koordinationschemie (siehe das Stereobild von [Ru(bpy)3]2+) aus mehreren Gründen stark zugenommen (mehrkernige Systeme, supramolekulare Strukturen und enantioselektive Katalysatoren). Hier wird an einer Vielzahl von Beispielen gezeigt, wie die Ligandenwahl die Konfiguration eines Metallzentrums oder die Chiralität eines Helicates vorherbestimmt.

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Stereospecific Influences in Metal Complexes Containing Optically Active Ligands. Part I. Some of the Optical Isomers of Tris-(propylenediamine)-cobalt(III) Ion

Cited by 108 publications

References 1 publication

Conformations of cyclic compounds in solution. V. Nuclear magnetic resonance study of the conformational preferences of some substituted ditertiary arsine chelate complexes of chromium carbonyl

Conformations of cyclic compounds in solution. V. Nuclear magnetic resonance study of the conformational preferences of some substituted ditertiary arsine chelate complexes of chromium carbonyl

Stereochemistry of Coordination Compounds. From Alfred Werner to the 21st Century

Prädeterminierte Chiralität an Metallzentren

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