Synthesis and characterization of new Pt(II) and Pt(IV) orthometallated complexes incorporating 1-arylazo-2-ethyl sulfanyl benzene

Shee, Biswaranjan; Pratihar, Jahar Lal; Chattopadhyay, Surajit

doi:10.1016/j.poly.2006.02.015

Cited by 7 publications

(5 citation statements)

References 19 publications

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“…The synthesis of symmetrical azobenzene derivatives was effected by: (i) oxidation reactions of aromatic primary amines; [19][20][21][22][23][24][25][26][27][28][29][30] (ii) reduction reactions of aromatic compound having nitro groups; [32][33][34][35][36] (iii) diazo-coupling via diazonium salts; [54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71] and (iv) coupling reactions with arenediazonium salts. 100,101 The synthesis of dissymmetrical azobenzene derivatives was effected by: (i) oxidation reactions of aromatic primary amines; 31 (ii) coupling of primary arylamines with nitroso compounds (Mills reaction); [37][38][39][40][41][42][43][44][45][46]…”

Section: Discussionmentioning

confidence: 99%

“…[37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] Compound 52 was obtained starting from the nitroso compound 50 and the aniline derivative 51 in acetic acid at 60 C in quantitative yield (Scheme 20). 51 It was notable that, using the Mills reaction, different electron-withdrawing and -donating groups could be present in the ortho-, meta-, and para-positions of both the aromatic nitroso compounds and the aromatic amines.…”

Section: Coupling Of Primary Arylamines With Nitroso Compounds (Millsmentioning

confidence: 99%

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Azobenzenes—synthesis and carbohydrate applications

et al. 2009

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Section: Discussionmentioning

confidence: 99%

Section: Coupling Of Primary Arylamines With Nitroso Compounds (Millsmentioning

confidence: 99%

Azobenzenes—synthesis and carbohydrate applications

et al. 2009

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“…' ASSOCIATED CONTENT b S Supporting Information. Crystallographic information files (CIF) for 1aÀ4c, UVÀvisible, 1 HNMR, 13 CNMR, FTIR, and elemental analysis data for 1aÀ4c, crystal and refinement data for 2aM, powder diffraction analysis of palladacycles 1aÀ3c, and additional figures showing weak interactions for series 1À4. This information is available free of charge via the Internet at http://pubs.acs.org.…”

Section: ' Discussionmentioning

confidence: 99%

“…The chloride salts 1a , 2a , 3a , and 4a were synthesized according to reported methods. ,− In a typical synthesis, a 15 mL warm ethanolic solution (45 °C) of Na 2 PdCl 4 (∼250 mg, 0.85 mmol) was added dropwise to a 15 mL warm ethanolic solution of phenyl azo-thioether based tridentate ligand (∼185 mg, 0.81 mmol). After continuously stirring for one hour over a steam bath (∼90 °C), a residual powder and well separated shiny crystals appeared.…”

Section: Methodsmentioning

confidence: 99%

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Link between Isostructurality, Polymorphism, and Weak Interactions in Palladacycle Crystals: Chemical Insight

Singh

Ramanan

Bandyopadhyay

2011

Crystal Growth & Design

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The chemistry of organopalladium compounds is significant owing to the presence of the PdÀC bond and its utility in the organic synthesis. 1,2 The Pd(II)/Pd(0) oxidation state interchange is a well-known event in the catalytic studies of such compounds during organic synthesis. 3 Palladium(II) salts are known to form PdÀC bonds with bidentating azobenzenes (C, N) and tridentating thioazobenzenes (C, N, S), which are commonly referred to as palladacycles. 4,5 Such palladium complexes have been extensively studied for CÀH bond activation and ArÀPd f ArÀOÀPd transformations. 6,7 Organopalladium compounds are also known to act as effective diagnostic probes in metalloporphyrin catalyzed oxidation reactions. 7,8 In these studies it has been frequently observed that the substitution at the phenyl ring drastically alters the diagnostic properties of the palladacycles. In a few cases, the solvent also plays a significant role in the regioselective reactions on PdÀC bonds. 9,10 In order to ascertain the nature of these catalytically active molecules, we have attempted crystallization to isolate them as solids and subject them to unambiguous structural elucidation. We have reported the presence of two polymorphs in the case of chlorido-{4-chloro-1-[2-(methylsulfanyl)-phenyldiazenyl]phenyl-k 3 C,N, S}-palladium(II). 11,12 Crystal structure analysis of these two polymorphs suggests that competing CÀH 3 3 3 Cl synthons are probably responsible for its occurrence. It remains an interesting point to address how the substituent on the ligand affects the solution and solid state properties of the palladacycles. Hence, we have judiciously designed a synthetic protocol to crystallize several palladacycle based salts, [X{4-R-1-[2-(R 0 -sulfanyl)-phenyldiazenyl]phenyl-k 3 C,N,S}-palladium(II)] where R = H, Cl and Me, R 0 = Me and Et, and X = Cl, Br, I, NO 3 , and ClO 4 . The paper reports the synthesis, characterization and crystal packing analysis of all solids. We also investigate the directional characteristics of CÀH 3 3 3 X interactions in dictating isostructures and polymorphs in the reported series.' EXPERIMENTAL SECTION Synthesis. The chloride salts 1a, 2a, 3a, and 4a were synthesized according to reported methods. 5,13À15 In a typical synthesis, a 15 mL warm ethanolic solution (45 °C) of Na 2 PdCl 4 (∼250 mg, 0.85 mmol) was added dropwise to a 15 mL warm ethanolic solution of phenyl azothioether based tridentate ligand (∼185 mg, 0.81 mmol). After continuously stirring for one hour over a steam bath (∼90 °C), a residual powder and well separated shiny crystals appeared. The solid was filtered, washed with 25% ethanol in water, and dried in air. The total yields of the solids were in the range of 90À95% with respect to the initial ligand.A modified methodology was adopted for the synthesis of the bromide salts (1b, 2b, 3b, and 4b) and the iodide salts (1c, 2c, 3c, and 4c). In a typical synthesis, the chloride salt (∼100 mg, 0.27 mmol) was dissolved in 60À70 mL CH 3 CN and a slight excess of solid

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