Coordination Mode of the Zinc(II) and Cadmium(II) Cations with N‐(Diisopropoxyphosphoryl)thiobenzamide

Abstract

Reaction of the potassium salt of N‐(diisopropoxyphosphoryl)thiobenzamide (iPrO)2P(O)NHC(S)C6H5 (HL) with ZnII and CdII cations in aqueous EtOH leads to three different complexes: [Zn(L‐O,S)2] (1), [Cd2(L‐O,S)4] (2) and [Cd(HL‐O)2(L‐O,S)2] (3). The structures of these compounds were investigated by single‐crystal X‐ray diffraction analysis, EI‐MS and ES‐MS, IR, 1H, 13C and 31P NMR spectroscopy and microanalysis. The zinc(II) atom in complex 1 is in a distorted tetrahedral ZnO2S2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. The cadmium(II) complex 2 is centrosymmetric and consists of dimeric species. Two [Cd(L‐O,S)2] moieties are connected by two bridging [S–Cd–S] units through the sulfur atoms of the ligand C=S groups. Complex 2 has a distorted trigonal‐bipyramidal Cd(Oax)2(Seq)3 core. Complex 3 has a tetragonal‐bipyramidal environment, Cd(Oax)2(Oeq)2(Seq)2, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in a typical 1,5‐O,S coordination mode. The ligands are in a trans configuration. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

C–Cl bond cleavage of CH2Cl2 by the zinc(II) complex [Zn(phen)L2] with the formation of [Zn(phen)LCl] and CH2[PhC(S)NP(O)(OiPr)2]2

“…Bond lengths (S)C-N (Dd % À0.07 Å) and P-N (Dd % À0.04 Å) are shortened (Table 2) and the C@S (Dd % 0.08 Å) and P@O (Dd % 0.02 Å) distances are considerably lengthened in comparison with the corresponding interatomic distances reported for HL [10]. The vice versa situation is observed for the same interatomic distances in comparison with the complex [ZnL 2 ] [7]. The bond lengths distribution in the ligand L confirms the superiority of S-enolic tautomeric form S-C@N-P@O.…”

“…N-Phosphorylated thiobenzamide HL, and complexes [ZnL 2 ], [Zn(bipy)L 2 ] and [Zn(phen)L 2 ] were prepared according to previously described methods [2,6,7]. Complex [Zn(phen)LCl] and S,S 0 -bis(benzimidothio-N-diisopropoxyphosphoryl)methane L-CH 2 -L were prepared by the following procedure: a suspension of [Zn(phen)L 2 ] in CH 2 Cl 2 (10 mL) was stirred for 3 h, and after few days colourless crystals of the complex were isolated (Scheme 1).…”

“…Recently, we have reported on complexes of Zn(II) with RC(S)NHP(O)(OiPr) 2 ligands (R = Ph, p-BrPh, NH 2 , iPrNH, tBuNH, c-C 6 H 11 NH, Et 2 N, c-C 5 H 10 N, c-OC 4 H 8 N, PhNH, p-MeOPhNH, p-BrPhNH) [1], and interaction of some of these complexes with 2,2 0 -bipyridine (bipy) and 1,10-phenanthroline (phen) [2]. The appearance of the hard donor carbonyl or phosphoryl oxygen atoms in the coordination sphere of the central ion makes it coordinatively unsaturated, which, in turn, can lead to the formation of heteroligand or polynuclear complexes with the central atom having the coordination number 5 or 6.On the other hand a promising strategy for inorganic crystal engineering through combining noncovalent bonds such as van der Waals, pÁ Á Áp stacking and hydrogen bonds with coordination chemistry has attracted increasing attention in recent years [3][4][5].In this work, we report on the synthesis of [Zn(phen)LCl] and L-CH 2 -L ðL ¼ PhCðSÞNPðOÞðOiPrÞ À 2 Þ using the reaction of the starting complex [Zn(phen)L 2 ] with CH 2 Cl 2 .N-Phosphorylated thiobenzamide HL, and complexes [ZnL 2 ], [Zn(bipy)L 2 ] and [Zn(phen)L 2 ] were prepared according to previously described methods [2,6,7]. Complex [Zn(phen)LCl] and S,S 0 -bis(benzimidothio-N-diisopropoxyphosphoryl)methane L-CH 2 -L were prepared by the following procedure: a suspension of [Zn(phen)L 2 ] in CH 2 Cl 2 (10 mL) was stirred for 3 h, and after few days colourless crystals of the complex were isolated (Scheme 1).…”

Complexes of Crown Ether‐Containing N‐Phosphorylated Thioamides and Thioureas with CoII, ZnII and PdII Cations

“…The intensities of the [M 2 L 3 ] + peak in the electrospray spectra of 1 – 3 are following: 43 % ( 1 ), 47 % ( 2 ), 67 % ( 3 ). Dimerization of complexes can be caused by formation of bridging bonds with participation of donor atoms of a ligand that is similar to complexes of Cd II , described in 12. However, the dimeric forms of complexes 1 – 3 are unstable in solutions and have composition ML 2 .…”

Complexes of crown-containing N-thioacylamido(thio)phosphates with Zn(II) and Co(II) cations

“…The intensities of the [M 2 L 3 ] + peak in the electrospray spectra of 1-3 are the following: 43% (1), 47% (2), and 67% (3). Dimerization of complexes can be caused by the formation of bridging bonds with participation of donor atoms of a ligand, that is similar to complexes of Cd(II), described in [14]. However, the dimeric forms of complexes 1-3 are unstable in solutions and dissociate with formation of monuclear ML 2 chelates.…”