Spectroscopic Properties of Luminescent Platinum(II) Complexes Containing 4,4‘,4‘ ‘-Tri-tert-butyl-2,2‘:6‘,2‘ ‘-terpyridine (tBu3tpy). Crystal Structures of [Pt(tBu3tpy)Cl]ClO4and [Pt(tBu3tpy){CH2C(O)Me}]ClO4

1999 ◽  
Vol 38 (19) ◽  
pp. 4262-4267 ◽  
Author(s):  
Siu-Wai Lai ◽  
Michael C. W. Chan ◽  
Kung-Kai Cheung ◽  
Chi-Ming Che
Keyword(s):  
Crystal Structures ◽  
Spectroscopic Properties ◽  
Tert Butyl

Cyclisierung von Di(tert-butyl-methyl)ketazin zu 1,2-Diaza-3-bora- und 1,2-Diaza-3-sila-cyclopent-5-enen / Cyclization of Di(tert-butyl-methyl)ketazine to 1,2-Diaza-3-bora- and 1,2-Diaza-3-sila-cyclopent-5-enes

2006 ◽  
Vol 61 (10) ◽  
pp. 1261-1274 ◽  
Author(s):  
Florian Armbruster ◽  
Nina Armbruster ◽  
Uwe Klingebiel ◽  
Mathias Noltemeyer ◽  
Stefan Schmatz
Keyword(s):  
Crystal Structures ◽  
Quantum Chemical Calculations ◽  
Chlorine Atom ◽  
Quantum Chemical ◽  
Membered Ring ◽  
Substitution Product ◽  
Tert Butyl ◽  
Isomeric Structures

The results of quantum chemical calculations on lithium ketazides suggest mainly four isomeric structures with different modes of lithium coordination (A-D). A monolithium ketazide thf-adduct (1) was isolated supporting the results of the quantum chemical calculations. In reactions of the lithiated di(tert-butyl-methyl)ketazine with BCl3 and Cl2BPh, 1,2-aza-azonia-3-borata-cyclopent-5-enes (2, 3) were isolated. Substitution of a chlorine atom of 2 and 3 with t-BuLi leads to the formation of derivatives 4 and 5. HCl elimination from 2 with Et3N gives - via a diazaboracyclopentene (6) - a bicyclus 7. In the reaction of the dilithiated ketazine with F2BN(SiMe3)2, the diaza-boracyclopentene 8 is obtained while with Cl4Si, F3SiN(SiMe3)2, and Cl2SiMe2 the diazasilacyclopentenes 9 - 11 are generated. SiF4 reacts with the dilithium ketazide to give a spirocyclus (12). The monolithium ketazide and Cl2SiMe2 react at 30 °C to give a four-membered ring isomer of the substitution product which is formed via a 1,3-chlorine shift from silicon to carbon (13). A tetrameric silanolate was isolated as a by-product in this reaction. It gives evidence for the structure of lithium ketazide A. Crystal structures of 5, 7, 10, and 14 are reported.

Five-coordinate copper(II) complexes: crystal structures, spectroscopic properties and new extended structural pathways of [Cu(chelate)2 X]Y, where chelate = dpyam, phen and bipy; X = pseudohalide ligands

2008 ◽  
Vol 64 (3) ◽  
pp. 318-329 ◽  
Author(s):  
Sujittra Youngme ◽  
Pongthipun Phuengphai ◽  
Chaveng Pakawatchai ◽  
Palangpon Kongsaeree ◽  
Narongsak Chaichit
Keyword(s):  
Crystal Structure ◽  
Size Effect ◽  
Crystal Structures ◽  
Direct Observation ◽  
Spectroscopic Properties ◽  
Modes Of Vibration

The crystal structures of four distortion isomers of the [Cu(chelate)2 X]+ cation, where chelate = 2,2-bipyridine (bipy), 1,10-phenanthroline (phen) and di-2-pyridylamine (dpyam), X = a pseudohalide ligand (NCO, NCS, N3 and C2N3), have been compared by scatterplot analysis with 25 [Cu(chelate)2 X]Y complexes of known crystal structure. The four new complexes [Cu(phen)2NCO]Br (1), [Cu(phen)2N3]BPh4·H2O (2), [Cu(dpyam)2(N3)]NO3·H2O (3) and [Cu(dpyam)2(N3)]ClO4 (4) involve a near regular square-based pyramidal stereochemistry (RSBP). The structures of complexes (1) and (2) are of the rare cases found for the phen analogue. Scatterplots of the 29 cation distortion isomers of the [Cu(chelate)2 X]Y series of complexes suggest that most of the 29 complexes lie on a common structural pathway, involving a mixture of the symmetric, C 2, and the asymmetric, non-C 2, in-plane modes of vibration of the CuN4N′ chromophore. Some datapoints are found to lie on extended routes The resulting structural pathways are consistent with the direct observation of the effect of the modes of vibration on the stereochemistries of the complexes. A comparison of the trends in the 29 datasets suggests a size effect of the phen, bipy and dpyam ligands.

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