Issue 44, 2010

Push-Pull Nitrile Ligands Exhibit Specific Hydration Patterns

Abstract

The reaction between K[PtCl3(Me2SO)] or prepared in this work cis- and trans-[PtCl2(NCNR2)(Me2SO)] (R2 = Me2,1; C4H8O, 2; C5H103) with an excess of NCNR2 in water gives the cationic bischelate [Pt{κ2-N,N′′′-NH[double bond, length as m-dash]C(NMe2)OC(NMe2)[double bond, length as m-dash]NH}2]2+ (42+) and the monochelates [PtCl{κ2-N,O-NH[double bond, length as m-dash]C(NR2)NC(NR2)[double bond, length as m-dash]O}(Me2SO)] (R2 = C4H8O, 5; C5H10, 6). Complex 42+ was released from the reaction mixture as 4·[PtCl3(Me2SO)]2·(H2O)2 or it was precipitated as 4·[A]2 (A = pic, 4·[pic]2; PF6, 4·[PF6]2; BPh4, 4·[BPh4]2·(NH2CONMe2)) by addition of picric acid, NaPF6, or NaBPh4, respectively, to the filtrate obtained after separation of 4·[PtCl3(Me2SO)]2·(H2O)2. In 2, the dialkylcyanamide ligand undergoes bond cleavage giving the known trans-[PtCl2{N(H)C4H8O}(Me2SO)] (trans-7). All complexes were characterized by elemental analyses (C, H, N), high resolution ESI-MS, IR, 1H and 13C{1H} NMR spectroscopic techniques, including 2D NMR correlation experiments (1H,1H-COSY, 1H,13C-HMQC/1H,13C HSQC, 1H,13C-HMBC, and 1H,1H-NOESY). The structures of cis-1, cis-3, 4·[PtCl3(Me2SO)]2·(H2O)2, 4·[BPh4]2·(NH2CONMe2) and 5 were determined by a single-crystal X-ray diffraction.

Graphical abstract: Push-Pull Nitrile Ligands Exhibit Specific Hydration Patterns

Supplementary files

Article information

Article type
Paper
Submitted
23 Jun 2010
Accepted
19 Aug 2010
First published
13 Oct 2010

Dalton Trans., 2010,39, 10790-10798

Push-Pull Nitrile Ligands Exhibit Specific Hydration Patterns

T. B. Anisimova, N. A. Bokach, K. V. Luzyanin, M. Haukka and V. Yu. Kukushkin, Dalton Trans., 2010, 39, 10790 DOI: 10.1039/C0DT00711K

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