A convenient route to dinuclear chloro-bridged platinum(ii) derivatives vianitrile complexes

Abstract

The syntheses of the complexes [PtCl(2)(NCR)L] [R = Me, Et; L = PPh(3); R = Et, L = Py, CO] and [PtCl{(κ(2)-P,C)P(OC(6)H(4))(OPh)(2)}(NCEt)] are described starting from the easily available [PtCl(2)(NCR)(2)]. The stability of the products under different experimental conditions is discussed as well as their use as precursors to dinuclear complexes [Pt(μ-Cl)ClL](2). The crystal and molecular structures of cis-[PtCl(2)(NCEt)(PPh(3))], [SP-4-2]-[PtCl{(κ(2)-P,C)P(OC(6)H(4))(OPh)(2)}(NCEt)] and trans-[Pt(μ-Cl){(κ(2)-P,C)P(OC(6)H(4))(OPh)(2)}](2) are reported.

Platinum(II) complexes containing unsaturated ligands. Nucleophilic substitution versus nucleophilic attack to ligand: a stereochemistry driven outcome

“…1 H NMR (CDCl 3 , T = 50°C): 7.80-7.20 (15H); 4.30 (m, 1H); 3.78 (br s, 1H); 3.37-2.85 (m, 6H); 2.41 (m, 1H); 1.64 (t, 3H); 1.52 (t, 3H); 0.82 (t) and 0.78 (t, 6H). 13 C NMR (CDCl 3 ): 167.7; 134.5 (d, J C-P = 11 Hz); 130.5 (d, J C-P = 61 Hz); 130.4; 127.9 (d, J C-P = 11 Hz); 48. 5; 47.7; 43.5; 38.7; 15.0; 14.0; 13.8.…”

“…2 (0.14 mmol of platinum) was suspended in 50.0 mL of MeCN at 0°C. A yellow solution was formed in 8 h ( 31 P NMR: trans-[PtCl 2 (NCMe)(PPh 3 )], 4.3 ppm, 1 J P-Pt = 4076 -Hz; traces of the cis-isomer were present) [13]. The solution was concentrated under vacuum (15 mL), cooled (À30°C) and treated, under stirring, with 0.017 mL of diethylamine (0.17 mmol, NHEt 2 / Pt molar ratio = 1.2).…”

“…cis-[PtCl 2 (PPh 3 )(NCMe)], cis-[PtCl 2 (PPh 3 )(NCEt)] and cis-[PtCl 2 (CO)(NCEt)] were prepared according to already reported procedures. [13] cis-[PtCl 2 (CO)(PPh 3 )] [14] was prepared (91% yield) by treatment of a propionitrile solution of cis-[PtCl 2 (NCEt)(PPh 3 )] with CO (P CO % 1 atm) at room temperature until complete conversion of the precursor was achieved (24 h, monitored by 31 P NMR spectroscopy). 31 P NMR: 10.9 ( 1 J P-Pt = 3030 Hz).…”

“…Elemental analyses (C, H, N) were performed at Dipartimento di Scienze e Tecnologie Chimiche, Università di Udine.trans-[PtCl 2 (C 2 H 4 )(NCEt)] was prepared from trans-[Pt(l-Cl)Cl(C 2 H 4 )] 2 according to the procedure described for trans-[PtCl 2 (C 2 H 4 )(NCMe)] [10,11]. cis-[PtCl 2 (C 2 H 4 )(NCMe)] was prepared (54% yield) by reacting a suspension of [Pt(l-Cl)Cl(C 2 H 4 )] 2 with an excess of MeCN (11.5 mmol) 13 C NMR (CD 3 CN): 74.8 ( 1 J Pt-C = 163 Hz, CH 2 = CH 2 ); 4.6 (CH 3 CN) in agreement with the literature data [12]. 195 Pt NMR (CD 3 CN): À2883 ( 1 J Pt-N = 364 Hz).…”

“…The solution turned deep yellow and was refluxed until the complete conversion of the precursor was achieved (2 h, monitored by 31 P NMR spectroscopy). The solvent was eliminated under vacuum, the solid residue was dissolved in 1,2-DCE (10 mL), treated with heptane (15 mL) and cooled (À30°C 13 …”