The Role of an Alkyl-Phenyl Spacer on the Reactivity of Novel Platinum(II) Complexes with Thiourea Nucleophiles

Abstract

The presented work, submitted as a paper, deals with the substitution reactions of mononuclear and dinuclear platinum(II) complexes of di‐2‐pyridylaminodiaquaplatinum(II), (Pt1); di‐2‐pyridylaminomethylbenzenediaquaplatinum(II), (Pt2); 1,2‐bis(di‐2‐pyridylaminomethyl)benzenetetraquaplatinum(II), (Pt3); 1,3‐bis(di‐2‐pyridylamino‐methyl)benzenetetraquaplatinum(II), (Pt4); and 1,4‐bis(di‐2‐pyridylaminomethyl)‐benzenetetraquaplatinum(II), (Pt5). These reactions were carried out on aqua complexes by three nucleophiles, viz., thiourea, N,N′‐dimethylthiourea, and N,N,N′N′‐tetramethylthiourea under pseudo–first‐order conditions as a function of nucleophile concentration and temperature by stopped‐flow and UV–visible spectrophotometric techniques. In addition, some DFT calculation was performed. The activation parameters support an associative substitution mechanism.

Non-conventional synthesis and photophysical studies of platinum(ii) complexes with methylene bridged 2,2′-dipyridylamine derivatives

“…The number of studies on alkylsubstituted di(2-pyridyl)amines is rather limited, 12,13 whereas methylene bridged aromatic derivatives receive more attention recently (Scheme 1, right). Inherent flexibility provided by the methylene linker not only expands the range of possibilities for various supramolecular motifs in solid state, as studied by L. Lindoy et al, [22][23][24] but also allows for non-trivial reactivity 25 and luminescent properties 26,27 of these compounds and their metal complexes. Compared to their conjugated counterparts, methylene bridged dpa derivatives are much easier to synthesize from dpa and corresponding halides via nucleophilic substitution reaction in presence of a base.…”

Tuning the Reactivity and Bonding Properties of the Pt(II) Complexes by the Substitution(s) on the Trans‐Coordinated Non‐Aromatic Amine Ligand

“…[11][12][13][14][15][16] In the third generation Pt(II) drugs the two amines are substituted by hydrocarbonamine groups mostly forming a divalent chelate. The effects of the non-leaving ligand(s) modifications have also been investigated but mostly on aromatic systems [17] and/or the interest has been focused on their antiproliferative and anticancer activities. [18][19][20][21][22] Kinetic aspects of non-aromatic non-leaving ligands have been explored less frequently [23][24][25] being often compared with the NH 3 groups in cisplatin.…”