Pd[tBuNH(S)NHP(O)(OiPr)2-S]2Cl2 complex as air- and moisture-stable catalyst for palladium catalyzed suzuki cross-coupling reaction

A highly efficient Suzuki cross-coupling reaction between phenyl bromide and phenylboronic acid catalyzed by the palladium complex Pd[tBuNH(S)NHP(O) (OiPr)2-S]2Cl2 in acetonitrile, toluene, THF or DMF has been investigated. The bases we have employed for this reaction were Na2CO3, K2CO3 or Cs 2CO3. It was established that using DMF and K 2CO3 at 100 °C shows excellent yields of the product at the catalyst amount of 0.1 mmol. The cross-coupling reactions of iodo- and chloro-benzene with phenylboronic acid were also investigated. The influence of the halide nature was as expected. © 2009 Springer Science+Business Media, LLC

Zn(II), Co(II) and Ni(II) complexes of a phosphorylthiourea derivative of 4-[(EtO)2P(O)CH2]-C6H4-NHC(S)NHP(O) (OiPr)2

The reaction of O,O'-diisopropyl phosphorisothiocyanatidate, (iPrO) 2P(O)NCS, with diethyl-(4-aminobenzyl)phosphonate leads to the new N-phosphorylated thiourea derivative, 4-[(EtO)2P(O)CH 2]-C6H4NHC(S)NHP(O)(OiPr)2 (HL). The reaction of its potassium salt KL with Zn(II) or Co(II) in aqueous EtOH leads to the complexes of formulae M(L-O,S)2 (ZnL2, CoL 2). The metal cation in all complexes is coordinated by two deprotonated ligands through the sulfur atoms of the thiocarbonyl groups and the oxygen atoms of the phosphoryl groups. The reaction of KL with Ni(II) leads to the formation of two types of complexes: the blue Ni(L-N,S)2 complex, where the ligand is coordinated through the nitrogen atom of the phosphorylamide group and the sulfur atom of the thiocarbonyl groups and light red Ni(L-O,S)2 complex with the same coordination of L- anion as it was observed for ZnL2 and CoL2. According to UV/Vis spectral data, it was established that the metal cation of Ni(L-N,S) 2 is in a square-planar environment in CH2Cl2, whereas the Ni(L-O,S)2 complex shows features of tetrahedral complexes. © 2010 Institute of Organic Chemistry and Biochemistry

Complexes of [(iPrO)2P(O)NHC(S)NHCH2] 2CH2 with Co(II), Ni(II), Zn(II), and Pd(II): Reaction of [(iPrO)2P(O)NHC(S)NHCH2]2 with KOH leading to the imidazolidine-2-imine derivative

Reaction of O,O'-diisopropylphosphoric acid isothiocyanate (iPrO) 2P(O)NCS with NH2(CH2)nNH2 (n = 3, 2) leads to the N-phosphorylated bis-thioureas [(iPrO)2C(S)NHP(O) NH]2Z (Z = -(CH2)3, H2LI; -(CH 2)2, H2LII). Reaction of the potassium salt of H2LI with Co(II) and Zn(II) in aqueous EtOH leads to complexes of formula M 2(L-O,S)2. The metal cation in both complexes is coordinated by two deprotonated ligands through the sulfur atoms of the thiocarbonyl groups and the oxygen atoms of the phosphoryl groups. Reaction of K2LI with Ni(II) and Pd(II) in the same conditions leads to M 2(L-N,S)2 complexes. In both compounds, the metal center is found in a square-planar N2S2 environment formed by the C=S sulfur atoms and the P-N nitrogen atoms of two deprotonated ligands LI. Reaction of H 2LII with KOH leads to a product of heterocyclization, in which one of the thiourea fragments is retained. Compounds obtained were investigated by IR, UV-Vis, 1H and 31P NMR spectroscopy, and microanalysis. Copyright © Taylor & Francis Group, LLC

Complexes of N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2 (X = O, S) with cobalt(II), zinc(II), and cadmium(II). Crystal structure of Co[AdNHC(S)NP(S)(OiPr)2]2

Reaction of the potassium salts of N-(thio)phosphorylated thioureas of common formula AdNHC(S)N(H)P(X)(OiPr)2 (Ad = adamantyl; X = O, HL I ; X = S, HL II ) with Co(II), Zn(II), and Cd(II) cations in aqueous EtOH leads to M(L I,II -X, S) 2 chelate complexes. The Cd(II) complex Cd(L I ) 2 could not be isolated under analogous conditions because of its hydrolytic lability. The structure of the resulting compounds was studied by means of spectroscopy and microanalysis; in addition, the molecular structure of the complex Co(L II ) 2 was elucidated by single crystal X-ray diffraction analysis. The cobalt atom is in a tetrahedral S4 environment formed by the C=S and P=S sulfur atoms of two deprotonated ligands L II . The magnetic properties of Co(L I,II ) 2 were investigated and the photoluminescent properties of the complexes are also reported. © 2008 Springer Science+Business Media B.V

Complexes of podand-containing bis(dithiophosphonate) ligands with cobalt(II), nickel(II) and cadmium(II): Recognition of CH2Cl 2

Reaction of the potassium salts of podand-containing bis(dithiophosphonate) s [PhO(4-C6H4)P(S)(SH)OCH2CH2] 2O (H 2 L) with Co(II), Ni(II) and Cd(II) in aqueous EtOH leads to complexes of formulae M2(L-S,S')2. The structural formulae of the compounds were deduced by physico-chemical and spectroscopic methods. It was established that complex Ni 2 L 2 recognizes CH2Cl2. © 2008 Springer Science+Business Media B.V

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

Reaction of the potassium salts of N-acylamido(thio)phosphates [4′-benzo-15-crown-5]NHC(S)NHP(Y)(OiPr)2 (Y = S, HLI; Y = O, HLII) with Zn(II) and Co(II) cations in aqueous EtOH leads to complexes of formulae Zn(LI,II - S,Y)2 (Y = S, 1; Y = O, 2) and Co(LI-S,S′)2 (3), while interaction of the potassium salt of [4′-benzo-15-crown-5]C(S)NHP(O)(OiPr)2 (HLIII) with Zn(II) in the same conditions leads to a complex of composition Zn(HLIII)(LIII-S,O)2 (4). © 2006 Elsevier B.V. All rights reserved

The influence of the substituent [PhNHNH- and EtN(NH2)-] on the N-thiophosphorylated thiosemicarbazides RC(S)NHP(S)(OiPr)2 crystal design

Two N-thiophosphorylated thiosemicarbazides of the common formula RC(S)NHP(S)(OiPr)2 [R = PhNHNH- (1); EtN(NH2)- (2)] have been synthesized and characterized by IR, 1H and 31P spectroscopy, and the single crystal X-ray diffraction method. Single crystal X-ray diffraction studies showed the thiosemicarbazides form both intra- and intermolecular hydrogen bonds, which in turn lead to polymeric chain formation. Moreover, according to the X-ray data of the phenylsubstituted thiosemicarbazide, the formation of intermolecular H⋯η6-phenyl interactions were established. © 2008 Elsevier Ltd. All rights reserved

1,10-diaza-18-crown-ether, modified by phosphonate pendant arms - Synthesis, structure, and picrate extraction properties

Reaction of O,O′-diisopropyl-3-methyl-1,2-butadienylphosphonate with 1,10-diaza-18-crown-6 in the presence of a catalytic amount of iPrONa leads to the new crown-ether derivative, containing phosphonate pendant arms (L). The structure of the compound obtained was investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P{1H} NMR spectroscopy, and microanalysis. In the crystal structure the side arms of L are in an anti disposition relative to the macrocyclic cavity. It was established that phosphorylation of 1,10-diaza-18-crown-6 by allenylphosphonate results in an increase of extraction of NaPic and KPic, whereas LiPic and NH4Pic are extracted practically in the same level. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA

Nitrocellulose membrane, modified by RC(S)NHP(X)(OiPr)2 (X = S, R = PhNH; X = O, R = PhNH, Ph), for sorption extraction of cobalt cations

The complexation and extraction properties of RC(S)NHP(X)(OiPr)2 [X = S, R = PhNH (HLI); X = O, R = PhNH (HLII), Ph (HLIII)] towards cobalt cations were studied. The nitrocellulose membrane was used as a carrier for HLI-III. The maximal degree of extraction of cobalt cations from an aqueous solution is observed at pH = 7.8-8.4. It was established that complexes formed are kept in a water solution on a surface of the carrier and washed away in 96% aqueous ethanol. The membrane modified by HLI allows extraction and concentration of Co(II) selectively, while the modification by HLIII leads to the selective extraction of Co(III). Copyright © 2010 Taylor & Francis Group, LLC