Synthesis and characterization of [4‐{(CH₂O)₂CH}C₆H₄]₂Hg, [4‐(O=CH)C₆H₄]₂Hg and [(E)‐4‐(RN=CH)C₆H₄]₂Hg (R = 2′‐py, 4′‐py, 2′‐pyCH₂, 4′‐pyCH₂)

Abstract

The reaction of 4‐[(CH2O)2CH]C6H4Br (1) with n‐BuLi, followed by addition of HgCl2 to the in situ formed organolithium derivative, affords [4‐{(CH2O)2CH}C6H4]2Hg (2). Deprotection of the formyl groups of 2 in presence of p‐TsOH (p‐Ts = 4‐MeC6H4SO3) leads to [4‐(O=CH)C6H4]2Hg (3). Condensation reactions of 3 with 2‐aminopyridine (2‐pyNH2), 4‐aminopyridine (4‐pyNH2), 2‐aminomethylpyridine (2‐pyCH2NH2), and 4‐aminomethylpyridine (4‐pyCH2NH2), in CH2Cl2, affords the novel diorganomercury(II) compounds of type [(E)‐4‐(RN=C)C6H4]2Hg [R = 2′‐py (4), 4′‐py (5), 2'‐pyCH2‐ (6), 4′‐pyCH2 (7)]. Compounds 2 and 3 were useful precursors for the preparation of the corresponding homocoupling products [4‐{(CH2O)2CH}C6H4]2 (8) and [4‐(O=CH)C6H4]2 (9) in presence of catalytic amounts of palladium(II) acetate. Compounds 2–9 were characterized by multinuclear magnetic resonance (NMR) (1H, 13C{1H}, and 199Hg{1H}, when appropriate) and infrared (IR) spectroscopy and by mass spectrometry. The molecular structures of 3, 5, 6, 8, and 9 were determined by single‐crystal X‐ray diffraction.

Silver(i) complexes containing heteroleptic diorganochalcogen(ii) ligands

“…The starting materials, commercially available 4-(CHO)C 6 H 4 Br, n -BuLi, Se, S, N -benzoylglycine, sodium acetate, AgOTf and AgPF 6 , were used without additional purification, while 4-[(CH 2 O) 2 CH]C 6 H 4 Br 40 was prepared following literature methods. The solvents used for the preparation of the ligands were dried and distilled under an argon atmosphere by following standard procedures.…”

Metal Complexes Containing Homoleptic Diorganoselenium(II) Ligands: Synthesis, Characterization and Investigation of Optical Properties

“…The precursor [2-(O=CH)C 6 H 4 ] 2 Se ( 3 ) was prepared following the method previously described in the literature [ 25 ], while for [4-(O=CH)C 6 H 4 ] 2 Se ( 4 ), the method was adapted [ 26 ]. Even though the diorganoselenide 4 has previously been reported in the literature [ 27 ], we developed a new method for the synthesis of this compound and fully characterized it.…”

“…The starting materials, 2-(CHO)C 6 H 4 Br, 4-(CHO)C 6 H 4 Br, n -BuLi, N -benzoylglycine, sodium acetate, AgOTf, AgPF 6 and ZnCl 2 , were commercially available and were used without additional purification. Se(detc) 2 [ 51 ], 2-[(CH 2 O) 2 CH]C 6 H 4 Br, 4-[(CH 2 O) 2 CH]C 6 H 4 Br [ 26 ] and AuCl(tht) [ 52 ] were prepared following literature methods. The solvents used for the preparation of precursors 1 – 4 were dried following standard procedures and distilled under an argon atmosphere prior to use.…”