Comparative analysis of M–O, M–S and cation–π(arene) interactions in the alkali metal (Na+, K+, Rb+, Cs+) bis-dithiocarbamate salts of N,N′-dibenzyl-1,2-ethylenediamine

Abstract

The alkali metal (Na + , K + , Rb + , Cs + ) bis-dithiocarbamate (bis-dtc) salts of N,N 0 -dibenzyl-1,2ethylenediamine have been prepared from the reaction of N,N 0 -dibenzyl-1,2-ethylenediamine with carbon disulfide in the presence of two equivalents of the corresponding alkali metal hydroxide. Additionally, the analogous triethylammonium derivative has been obtained. The resulting compounds have been analyzed as far as possible by elemental analysis, FAB + mass spectrometry, IR, UV-Vis and NMR ( 1 H, 13 C) spectroscopy, and single-crystal X-ray diffraction, showing that the composition of the metal salts can be described by the general formula. The solid-state and solution studies showed that all alkali metal ions participate in the formation of M-O and cation-p(arene) interactions, while M-S interactions are only observed for the larger alkali metals K + , Rb + and Cs + . As expected, within the alkali metal group there is a clear tendency for a decreasing number of M-O bonds in favor of M-S and cation-p(arene) interactions, however, only K + forms a semi-sandwich type complex with h 6 -coordination.

Crystal structure of dipotassiumN-carbodithioato-L-prolinate trihydrate

“…The most frequently observed coordination pattern in dithiocarbamates of the heavier alkali metals (K, Rb and Cs) is a symmetric double-chelating mode, leading to a puckered S 2 M 2 ring (e.g. Howie et al, 2008;Reyes-Martínez et al, 2009;Mafud, 2012; see (B) in Fig. 3].…”

Crystal structure of a compact three-dimensional metal–organic framework based on Cs+and (4,5-dicyano-1,2-phenylene)bis(phosphonic acid)

“…Although unusual in the case of Cs, in the Cambridge Structural Database (CSD) a total of 45 structures in which coordination between the metal cation and the hydronium cation is present, e.g. among the metal complexes (Reyes-Martínez et al, 2009;Jennifer et al, 2014;Teng et al, 2016;Hu & Mak, 2013) and coordination polymer/metal-organic frameworks (Yotnoi et al, 2015;Wang et al, 2013;Humphrey et al, 2005). Wang et al (2013) in fact reported the structures of an isotypic series of crystal materials involving lanthanides (Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Y), in which the presence of the coordinating hydronium cation was confirmed.…”

Multimetallic complexes of group 10 and 11 metals based on polydentate dithiocarbamate ligands

“…8 This ligand is slightly unusual in that it has two different substituents on the nitrogen which contrasts with the symmetrical nature of most dithiocarbamate ligands. One literature report discusses the supramolecular contacts between the alkali metal salts of [L 1 ] 2-, 7 while another explores the linking of molybdenum oxo units. 8a The remaining paper focuses on the analysis of trace heavy metals using the ligand but does not report full spectroscopic data for the (presumably) homoleptic complexes formed.…”

“…These spectroscopic data can be compared to those for the symmetrical piperazine-based bis(dithiocarbamate) complex [(Et 3 P) 2 Pt(S 2 CNC 4 H 8 NCS 2 )Pt(PEt 3 ) 2 ](PF 6 ) 2 , 5e which displays only a singlet resonance in the 31 P NMR spectrum. In order to examine this inequivalence further, a variable 3) 2.2162 (7), Ni(2)-P(84) 2.2007(7), Ni(2)-S(10) 2.2100 (7), Ni(2)-P(61) 2.2213 (7), Ni(2)-S( 9) 2.2230 (7), S(1)-C(2) 1.727(3), C(2)-N(4) 1.316(3), C(2)-S(3) 1.711(2), N(7)-C(8) 1.314(3), C(8)-S( 9) 1.713(2), C(8)-S(10) 1.718(2), S(1)-Ni(1)-S(3) 78.41(2), S(10)-Ni(2)-S( 9) 78.27(2), S(3)-C(2)-S(1) 109.07(13), S(9)-C(8)-S(10) 109.31(13).…”

“…2 Molecular structure of the dication in 3. Selected bond distances (A ˚) and angles ( • ): Pd(1)-P(48) 2.2923(6), Pd(1)-P(25) 2.3018(6), Pd(1)-S(3) 2.3348(6), Pd(1)-S(1) 2.3516(6), Pd(2)-P(84) 2.2906(7), Pd(2)-P(61) 2.3110(6), Pd(2)-S(10) 2.3347(6), Pd(2)-S(9) 2.3445(7), S(1)-C(2)1.728(2), C(2)-N(4)1.313(3), C(2)-S(3)1.719(2), N(7)-C(8)1.323(3), C(8)-S(10)1.709(2), C(8)-S(9) 1.723(2), S(3)-Pd(1)-S(1) 75.07(2), S(10)-Pd(2)-S(9) 74.98(2), S(3)-C(2)-S(1) 111.88(14), S(10)-C(8)-S(9) 112.15(13).…”