AbstractDer Titelligand Lwird aus 3,3‐Dimethyl‐l ,5,8,l 1‐tetraazacyclotridecen‐(1)‐ Ni(II)‐tetrachlorozinkat durch Reaktion mit Na‐bicarbonat, Reduktion mit Na‐tetrahydridoborat, Reaktion mit Na‐cyanid sowie Ätherextraktion als Hydroperchlorat synthetisiert.
Chemischer InformationsdienstVolume 3, Issue 33 Preparative Organic Chemistry ChemInform Abstract: STRUKTURUNTERSUCHUNGEN AN KOORDINIERTEN MAKROCYCLISCHEN LIGANDEN 1. MITT. KRISTALL- UND MOLEKULARSTRUKTUR VON (1RS, 3SR, 8RS, 10SR)-3,5,7,7,10,12,14,14-OKTAMETHYL-1,4,8,11-TETRAAZA-CYCLOTETRADECADIEN-(4, 11)-NICKEL(II)-PERCHLORAT D. A. SWANN, D. A. SWANNSearch for more papers by this authorT. N. WATERS, T. N. WATERSSearch for more papers by this authorN. F. CURTIS, N. F. CURTISSearch for more papers by this author D. A. SWANN, D. A. SWANNSearch for more papers by this authorT. N. WATERS, T. N. WATERSSearch for more papers by this authorN. F. CURTIS, N. F. CURTISSearch for more papers by this author First published: August 15, 1972 https://doi.org/10.1002/chin.197233418AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume3, Issue33August 15, 1972 RelatedInformation
The preparation of the cyclic tetra-secondary amine 3,3-dimethyl-1,5,8,11-tetra-azacyclotridecane from the previously reported nickel(II) complex is described. Cobalt(III) complexes of the amine were prepared with the amine in planar (bcde-octahedral) and folded (abcd-octahedral) co-ordination. Derivatives of the complex cobalt cation in three configurations arising from restricted inversion at the four chiral co-ordinated secondary amino-groups were prepared. The relative stabilities of the possible configurations in planar and folded coordination are discussed, and assignments of configuration of the observed forms are made, based on chemical and physical (particularly 1H n.m.r. spectral) properties.
Nickel(II) complexes of 3,3-dimethyl- and 2,4,4-trimethyl-1,5,8,11-tetra-azacyclotrideca-1-ene and 3,3-dimethyl-1,5,8,11-tetra-azacyclotridecane are described. Singlet ground-state square-planar complexes are formed with poorly co-ordinating anions such as tetrachlorozincate. Triplet ground-state 'octahedral' complexes are formed with the co-ordinating anions oxalate, acetate, acetylacetonate (all as chelates) with thiocyanate and azide, and with diaminoethane. The three cations exist as configurational isomers, arising from restricted inversion at the asymmetric co-ordinated secondary amine centres.
AbstractDie Komplexkationen (I) (dargestellt aus Tetrachloro‐tris‐[triäthylentetramin]‐ dinickel) und ,der Komplex (II), der durch Hydrierung des Produktes (Ia) erhalten wird, existieren mit wenig koordinierend" wirkenden Anionen wie Tetrachlorozincat als quadratisch‐planare Komplexe.
Nickel(II) complexes of the isomeric cyclic tetraimines, 2,4,4,9,11,11-hexamethyl-1,5,8,12-tetra-azacyclotetradeca-1,5,8,12-tetraene and 2,4,4,9,9,11-hexamethyl-1,5,8,12-tetra-azacyclotetradeca-1,5,7,11-tetraene, have been prepared by the nitric acid oxidation of the appropriate (1,8- and 1,11-respectively) diene nickel(II) complexes. Both cations are reduced by aqueous borohydride or hydrogen with platinum catalyst to reform the diene complexes. The nickel(II) complex of the 2,4,4,9,9,11-hexamethyl isomer is reduced by hypophosphorous acid to yield the cyclic tri-iminemonoamine 2,4,4,9,9,11-hexamethyl-1,5,8,12-tetra-azacyclotetradeca-1,5,11-triene, as the nickel-(II) complex. Singlet ground-state square-planar derivatives, e.g. perchlorate salts, and triplet ground-state octahedrally co-ordinated derivatives, e.g. dithiocyanato-derivatives, are described. I.r., electronic, and n.m.r. spectra, and magnetic susceptibilities are reported.
Chemischer Informationsdienst. Organische ChemieVolume 1, Issue 40 Organoelement Compounds ChemInform Abstract: CYCLISCHE TETRAAMINE UND IHRE METALLKOMPLEXE 6. MITT. KRISTALLSTRUKTUR VON ACETATO-C-RAC.-(5,7,7,12,14,14-HEXAMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECAN)-NICKEL(II)-PERCHLORAT UND DES ANALOGEN CIS-OXALATOKOBALT(III)-DIPERCHLORATS P. O. WHIMP, P. O. WHIMPSearch for more papers by this authorMARCIA F. BAILEY, MARCIA F. BAILEYSearch for more papers by this authorN. F. CURTIS, N. F. CURTISSearch for more papers by this author P. O. WHIMP, P. O. WHIMPSearch for more papers by this authorMARCIA F. BAILEY, MARCIA F. BAILEYSearch for more papers by this authorN. F. CURTIS, N. F. CURTISSearch for more papers by this author First published: October 6, 1970 https://doi.org/10.1002/chin.197040049AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume1, Issue40October 6, 1970 RelatedInformation
The structure of acetato-C-rac-(5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane)nickel(II) perchlorate has been investigated by single-crystal three-dimensional X-ray methods. The blue prismatic crystals are monoclinic, space group P21/c, with a= 9·39, b= 30·67, c= 9·57 Å, β= 119·3°, Z= 4. The structure was solved by Patterson and Fourier syntheses, and refined by least-squares methods to a final R of 0·120 for the 2753 visually estimated independent reflexions.The cyclic tetra-amine is folded, with the four secondary amine groups co-ordinated to adjacent octahedral sites of the nickel (II) ion. The acetate ion functions as a symmetric chelate, occupying the two remaining sites. The cyclic tetra-amine is the C-rac-modification, and both pairs of asymmetric nitrogens also have the racemic arrangement, but the pairs are of opposite helicity.The relative energies of the 36 configurations of the co-ordinated 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane macrocycles, arising from the pair of asymmetric carbon centres and two pairs of asymmetric nitrogen centres, are discussed in terms of the conformational energies of the chelate ring systems and methyl substituent interaction energies.The space-group determination of cis-oxalato-C-rac-(5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane)cobalt(III) perchlorate is also reported: Pccn, with a= 16·03, b= 9·61, c= 15·12 Å, Z= 4.
The preparations of bis(hydroxyethylethylenediamine)copper(II) as the nitrate and perchlorate salts are reported. These compounds react with acetone to form copper(II) complexes of 1,15-dihydroxy-7,9,9-trimethyl-3,6,10,13-tetra-azapentadeca-6-ene. I.r. and visible–u.v. spectra are reported.
The preparations and properties of some octahedral cobalt(III) complexes of the C-meso and C-racemic isomers of the cyclic tetra-amine 5,7,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane (tetc and tetd), are described. Both isomers from trans-cobalt(III) derivatives with unidentate ligands occupying the axial co-ordination sites and, in addition, the isomer tetd, which is probably the meso form, can form cis derivatives such as [Co(tetd)C2O4]+. The trans derivatives [Co(tetc)XY]+(where X = Y = Cl–, CN–, NCS–, and NO2–; X = Cl–, Y = CH3CO2–), [Co(tetc)(H2O)2]3+, and [Co (tetd)Cl2]+, and the cis derivative [Co (tetd)C2O4]+, are described.
The preparations and properties of the following complexes of dipropylenetriamine [NH2·[CH2]3·NH·[CH2]3·NH2= dpt] are reported: Ni(dpt)2Cl2,H2O, Ni(dpt)2(NO2)3,H2O, Ni dpt (NO3)2, Ni dpt (NO3)2, (H2O)2, Ni dpt Cl2, Cu(dpt)2(ClO4)2, Cu dpt (dptH)(OH)(ClO4)2, Cu3(dpt)3(CO3)(ClO4)4,2H2O, Cu4(dpt)4(CO3)Cl6,8H2O, Zn(dpt)2(ClO4)2, Zn2(dpt)2OH(ClO4)3, Zn dpt Cl2, Co dpt Cl3, Co dpt (NCS)3, Co dpt (N3)3, Co dpt (NO2)3, and Co dpt Cl2(H2O)ClO4. Infrared spectra, metal-ion spectra, and magnetic susceptibilities (of the copper compounds) are reported.