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Issue 13, 2015
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Coupling of platinated triguanides with platinum-activated nitriles as a novel strategy for generation of dimetallic systems

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Abstract

One of two PtIV-activated propanenitriles in trans-[PtCl4(EtCN)2] is involved in platinum(IV)-mediated nitrile–imine coupling with the platinum(II)-based metallacycles [PtCl2{NH[double bond, length as m-dash]C(NR2)N(Ph)C([double bond, length as m-dash]NH)N(Ph)C(NR2)[double bond, length as m-dash]NH}] [R2 = Me2 (1a), C5H10 (1b)] yielding diplatinum products, whose structures depend on molar ratios between the reactants. At a 1 : 1 ratio, the mixed-valence platinum(II)/platinum(IV) species [PtCl4{NH[double bond, length as m-dash]C(NR2)N(Ph)C{[double bond, length as m-dash][(N(Et)C[double bond, length as m-dash]NH)PtCl2(EtCN)]}N(Ph)C(NR2)[double bond, length as m-dash]NH}] [R2 = Me2 (2a), (CH2)5 (2b)] were generated, whereas at a 1 : 2 ratio the dinuclear platinum(II)/platinum(II) complexes [PtCl2{NH[double bond, length as m-dash]C(NR2)N(Ph)C{[double bond, length as m-dash][(N(Et)C[double bond, length as m-dash]NH)PtCl2(EtCN)]}N(Ph)C(NR2)[double bond, length as m-dash]NH}] [R2 = Me2 (3a), (CH2)5 (3b)] were obtained. In contrast to the nitrile–imine coupling observed for the platinum(IV) dinitrile complex, the reaction between the platinum(II) congener trans-[PtCl2(EtCN)2] and any one of 1a,b gives exclusively the substituted dimetallic platinum(II)/platinum(II) products [PtCl2{NH[double bond, length as m-dash]C(NR2)N(Ph)C{[double bond, length as m-dash][(NH)PtCl2(EtCN)]}N(Ph)C(NR2)[double bond, length as m-dash]NH}] [R2 = Me2 (6a), (CH2)5 (6b)] featuring platinum-containing guanidine 1 as one of the ligands. Complexes 2a,b, 3a,b, and 6a,b were characterized by elemental analyses (C, H, N), HRESI-MS, IR, 1H NMR spectroscopy, and DTA/TG. The molecular and crystal structure of 2a·2CDCl3 was additionally studied by single-crystal X-ray diffraction. Complexes 2a,b undergo further redox transformation in solutions, and single crystals of [PtCl2{NH[double bond, length as m-dash]C(NMe2)N(Ph)C{[double bond, length as m-dash][(N(Et)C[double bond, length as m-dash]NH)PtCl2(MeCN)]}N(Ph)C(NMe2)[double bond, length as m-dash]NH}]·2CH2Cl2 (3′a·2CH2Cl2) were obtained from 2a in a CH2Cl2–MeCN–C2H4Cl2 mixture and studied by X-ray crystallography. The driving forces for the generation of diplatinum products 2 and 3 were elucidated based on a quantum-chemical study.

Graphical abstract: Coupling of platinated triguanides with platinum-activated nitriles as a novel strategy for generation of dimetallic systems

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Supplementary files

Article information


Submitted
16 Dec 2014
Accepted
08 Feb 2015
First published
11 Feb 2015

Dalton Trans., 2015,44, 6003-6011
Article type
Paper

Coupling of platinated triguanides with platinum-activated nitriles as a novel strategy for generation of dimetallic systems

T. V. Serebryanskaya, A. S. Novikov, P. V. Gushchin, A. A. Zolotarev, V. V. Gurzhiy and V. Yu. Kukushkin, Dalton Trans., 2015, 44, 6003
DOI: 10.1039/C4DT03870C

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