Palladium(II) Complexes of Bis(diphosphene) with the Different Coordination Behavior

2022 ◽  
Author(s):  
Rikako Ura ◽  
Akihiro Tsurusaki ◽  
Ken Kamikawa

Organophosphorus compounds possessing the P−P double-bond character are intriguing materials in coordination chemistry because it is possible to form a variety of coordination modes from the π-bond in addition to...

2015 ◽  
Vol 71 (12) ◽  
pp. o1086-o1087
Author(s):  
Ioannis Tiritiris ◽  
Willi Kantlehner

In the crystal structure of the title salt, C24H38N42+·2C24H20B−, the C—N bond lengths in the central CN3unit of the guanidinium ion are 1.3364 (13), 1.3407 (13) and 1.3539 (13) Å, indicating partial double-bond character. The central C atom is bonded to the three N atoms in a nearly ideal trigonal–planar geometry and the positive charge is delocalized in the CN3plane. The bonds between the N atoms and the terminal methyl groups of the guanidinium moiety and the four C—N bonds to the central N atom of the (benzyldimethylazaniumyl)propyl group have single-bond character. In the crystal, C—H...π interactions between the guanidinium H atoms and the phenyl C atoms of the tetraphenylborate ions are present, leading to the formation of a two-dimensional supramolecular pattern parallel to theacplane.


2012 ◽  
Vol 68 (6) ◽  
pp. o1812-o1812 ◽  
Author(s):  
Ioannis Tiritiris ◽  
Willi Kantlehner

The reaction of 3,3,3-tris(dimethylamino)-1-phenylprop-1-yne with bromine in pentane yields the title compound, C13H17N2 +·Br−. The acetylenic bond distance [1.197 (2) Å] is consistent with a C[triple-bond]C triple bond. The amidinium C=N bonds [1.325 (2) and 1.330 (2) Å] have double-bond character and the positive charge is delocalized between the two dimethylamino groups.


1955 ◽  
Vol 33 (1) ◽  
pp. 128-133 ◽  
Author(s):  
R. U. Lemieux ◽  
G. Huber

3,4,6-Tri-O-acetyl-β-D-glucopyranosyl chloride was found to undergo solvolysis in acetic acid to form 1,3,4,6-tetra-O-acetyl-α-D-glucopyranose as the main reaction product. The much less reactive anomeric α-chloride also appeared to undergo solvolysis with extensive inversion of the anomeric center. It is submitted that the tendencies for inversion obtained in these ionic reactions are due to the conformations imposed on the intermediate ions through distribution of the positive charge to the ring oxygen and the consequent introduction of double-bond character to the carbon-1 to ring-oxygen bond.


IUCrData ◽  
2016 ◽  
Vol 1 (1) ◽  
Author(s):  
Ioannis Tiritiris ◽  
Willi Kantlehner

The asymmetric unit of the title salt, 2C5H12N3O+·SO42−, comprises two cations and one sulfate ion. In both cations, the C, N and O atoms of the morpholine rings are disordered over two sets of sites, with refined occupancies of 0.849 (3):0.151 (3) for cation I and 0.684 (4):0.316 (4) for cation II. The C—N bond lengths in both central C3N units of the carboxamidinium ions range between 1.253 (12) and 1.362 (5) Å, indicating a degree of double-bond character. The central C atoms are bonded to the three N atoms in a nearly ideal trigonal–planar geometry and the positive charges are delocalized in both CN3planes. The crystal structure is stabilized by a three-dimensional network of N—H...O hydrogen bonds between the cations and the sulfate ion. Scheme tiny font, charges and delocalized bonds almost invisible


2015 ◽  
Vol 71 (12) ◽  
pp. o984-o985
Author(s):  
Ioannis Tiritiris ◽  
Stefan Saur ◽  
Willi Kantlehner

In the cation of the title salt, C6H14NO+·C24H20B−, the C—N bond lengths are 1.297 (2), 1.464 (2) and 1.468 (2) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.309 (2) Å shows double-bond character, pointing towards charge delocalization within the NCO plane of the iminium ion. In the crystal, C—H...π interactions between the iminium H atoms and the phenyl C atoms of the anion are present. The phenyl rings form aromatic pockets, in which the iminium ions are embedded.


2015 ◽  
Vol 71 (12) ◽  
pp. o1045-o1046 ◽  
Author(s):  
Ioannis Tiritiris ◽  
Willi Kantlehner

In the title salt, C15H36N62+·2C24H20B−, the three N—C bond lengths in the central C3N unit of the bisamidinium ion range between 1.388 (3) and 1.506 (3) Å, indicating single- and double-bond character. Furthermore, four C—N bonds have double-bond character. Here, the bond lengths range from 1.319 (3) to 1.333 (3) Å. Delocalization of the positive charges occurs in the N/C/N and C/N/C planes. The dihedral angle between both N/C/N planes is 70.5 (2)°. In the crystal, C—H...π interactions between H atoms of the cation and the benzene rings of both tetraphenylborate ions are present. The benzene rings form aromatic pockets, in which the bisamidinium ion is embedded. This leads to the formation of a two-dimensional supramolecular pattern along theabplane.


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