Structural and Spectroscopic Studies of [M((x)tu)₄]⁺ Systems (M = Cu, Ag; (x)tu = (substituted) Thiourea)

Abstract

In a low-temperature redetermination of improved precision of the structure of [Cu(tu) 4 ]

Synthesis and Characterization of Coordination Compounds of Silver(I) Nitrite with Ligands Ethylenethiourea and N,N'-diethylthiourea

“…This is evidenced by the Griess Illosvay test and produced a red solution for coordination compound A, and colourless solution for compound B. The resulting coordination compounds A and B were found colorless needle and prism crystals, as shown in Figure 1 [8]. Silver atom with four coordination number with square planar structure has never been reported despite having a negative free energy.…”

“…Coordination compound of AgNO 3 and etu has been synthesized in 1 : 4 and reported as [Ag (etu) 4 ](NO 3 )·H 2 O [7]. Etu coordinated through sulfur atom as dimer coordination compound and forming distorted tetrahedral geometry about silver atom [8].…”

Heterocyclic‐2‐thione Derivatives of Silver(I): The Methyl Substituent at N1atom of a Imidazoline‐2‐thione/Imidazolidine‐2‐thione Alters a Dimer [Ag2(HL)4(PPh3)2](NO3)2 into a Monomer [Ag(HL)2(PPh3)](NO3)

“…In literature reports, heterocyclic thiones with silver(I) salts have yielded complexes of different nuclearity, which can be gauzed from the types of compounds (Scheme for ligands) listed below: (a) two coordinate complexes, [Ag(L I ‐NH‐ S ) 2 ](ClO 4 ),15 [Ag(L I ‐N R ‐ S ) 2 ](F 3 CSO 3 ) · CH 2 Cl 2 ( R = 4‐MeO–C 6 H 4 –);16 (b) trigonal planar complexes, [Ag(SCN)(L I ‐NH‐ S ) 2 ],17 [Ag(PPh 3 ) 2 (L VI ‐NH‐ S )](NO 3 ),18 [Ag(L I ‐NH‐ S ) 3 ] 2 (SO 4 ),19 [Ag(L II ‐NMe‐ S ) 2 (PPh 3 )] X ( X = 4‐benzoyl‐3‐methyl‐1‐phenylpyrazol‐5‐olate);20 (c) mononuclear tetrahedral complexes, [AgCl(L‐NR‐ S )(PPh 3 ) 2 ] (L‐N R = L I ‐NH, L II ‐NMe, L III ‐NH, L V ‐NH, L VI ‐NH),19,21–23 [Ag(L‐NR‐ S ) 2 (PPh 3 ) 2 ](NO 3 ) (L‐N R = L V ‐NH, L VII ‐NH),18,24 [Ag(L‐N R ‐ S ) 4 ] X {L‐N R = L I ‐NH, L V ‐NMe; X = NO 3 ,ClO 4 , BF 4 },15,25,26 [AgCl(L I ‐NH‐ S ) 3 ],27 [Ag(L V ‐NH‐ S ) 2 L′ 2 ](NO 3 ) [L′ = 2‐(diphenylphosphanyl)phenyl)‐ether];28 (d) halogen‐bridged dinuclear complexes, [Ag 2 (μ‐Br) 2 (L VI ‐NH‐ S ) 2 (PPh 3 ) 2 ],29 [Ag 2 (μ‐Br) 2 (L I ‐NH‐ S ) 4 ],19,30 sulfur‐bridged dimers [Ag 2 X 2 {μ‐(L V ‐NH‐ S )} 2 (PPh 3 ) 2 ] ( X = Cl, Br),31 [Ag 2 {μ‐(L III ‐NH‐ S )} 2 (L III ‐NH‐ S ) 2 (PPh 3 ) 2 ](NO 3 ) 2 ,22 [Ag 2 {μ‐(L I ‐NH‐ S )} 2 (L I ‐NH‐ S ) 4 ]) X 2 ( X = NO 3 , ClO 4 );19 and (e) polynuclear complexes such as [Ag(L I ‐NH‐ S ) {μ‐(L I ‐NH‐ S )} 2 Cl] n , [Ag 2 {μ‐(L II ‐NMe‐ S )}(μ 3 ‐I) 2 ] n , {Ag(L V ‐NH‐ S )Cl} n and with several other silver salts. [27,30,32–43]…”

Structural and spectroscopic studies of some adducts of silver(i) halides with thiourea and N-ethyl substituted thioureas

“…Thus, while four unidentate S-coordinated thiourea ligands are found in the hexafluorosilicate(IV) salt, [Cu(tu) 4 ](SiF 6 ) 2 , 11-13 no counterpart [Ag(tu) 4 ] + example has yet been so defined for silver(I), the highest AgX:tu stoichiometry thus far structurally authenticated being 1 : 3, 14 although formation of a complex [Ag(etu) 4 ]NO 3 was claimed in an early study, 15 and recently authenticated crystallographically. 13 Adducts AgX:xtu (1 : 3) may be found in mononuclear or binuclear form. The latter are found with non-or feeblycoordinating anions as ionic [(xtu) 2 Ag(m-S-xtu) 2 Ag(xtu) 2 ] 2+ arrays, for adducts of silver(I) perchlorate with tu, 16 dmtu, 17 etu, 18 ('dmtu' = (MeHN) 2 CS).…”