Issue 41, 2012
From the journal:

Dalton Transactions

Reactions of platinum(iv)-bound nitriles with isomeric nitroanilines: addition vs. substitution†

Alexander N. Chernyshev,ab   Nadezhda A. Bokach,*a   Pavel V. Gushchin,a   Matti Haukka*b  and  Vadim Yu. Kukushkin*ac  

* Corresponding authors

a Department of Chemistry, St. Petersburg State University, Universitetsky Pr. 26, 198504 Stary Petergof, Russian Federation
E-mail: bokach@nb17701.spb.edu, kukushkin@vk2100.spb.edu

b University of Jyväskylä, Department of Chemistry, P.O. Box 35, FI-40014 University of Jyväskylä, Finland
E-mail: matti.o.haukka@jyu.fi

c Saint Petersburg State Forest Technical University, Institutsky per. 5, 194021 St. Petersburg, Russian Federation

Abstract

The platinum(IV) complex trans-[PtCl4(EtCN)2] reacts smoothly and under mild conditions with isomeric o-, m- and p-nitroanilines (NAs) yielding two different types of products depending on the NA isomer, viz. the nitroaniline complexes cis/trans-[PtCl4(NA)2] (cis/trans-1–3) and the amidine species trans-[PtCl4{NH[double bond, length as m-dash]C(Et)NHC6H4NO2-m}(EtCN)] (4), trans-[PtCl4{NH[double bond, length as m-dash]C(Et)NHC6H4NO2-m}2] (5) and trans-[PtCl4{NH[double bond, length as m-dash]C(Et)NHC6H4NO2-p}(EtCN)] (6). Complexes 4 and 5 undergo cyclometalation, furnishing mer-[PtCl3{NH[double bond, length as m-dash]C(Et)NHC6H3NO2-m}(EtCN)] (7) and mer-[PtCl3{NH[double bond, length as m-dash]C(Et)NHC6H4NO2-m}{NH[double bond, length as m-dash]C(Et)NHC6H3NO2-m}] (8), respectively. Moreover, 8 both in the solid state and in solution undergoes the second step of the cyclometalation, generating [PtCl2{NH[double bond, length as m-dash]C(Et)NHC6H3NO2-m}2] (9). In 4, the nitrile ligand is highly reactive toward nucleophilic addition and it undergoes facile hydration accompanied by the elimination of the nitrile, thus producing cis-[PtCl4(NH2C6H4NO2-m){NH[double bond, length as m-dash]C(OH)Et}] (10), or methanol addition providing trans-[PtCl4{NH[double bond, length as m-dash]C(Et)NHC6H4NO2-m}{NH[double bond, length as m-dash]C(Et)OMe}] (11). All compounds, besides 9, were characterized by C, H, and N elemental analyses, high-resolution ESI-MS, IR, 1H and 13C{1H} NMR spectroscopic techniques. Complex 9, which was not isolated as a pure compound, was identified in the reaction mixture by ESI-MS and 1H and 13C{1H} NMR spectroscopies. Complexes trans-1, trans-2, 4, 5, 6, 8, 10, and 11 were additionally studied by X-ray diffraction.

Graphical abstract: Reactions of platinum(iv)-bound nitriles with isomeric nitroanilines: addition vs. substitution

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Article information

DOI
https://doi.org/10.1039/C2DT30986F
Article type
Paper
Submitted
06 May 2012
Accepted
24 Aug 2012
First published
28 Aug 2012

Dalton Trans., 2012,41, 12857-12864

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Reactions of platinum(IV)-bound nitriles with isomeric nitroanilines: addition vs. substitution

A. N. Chernyshev, N. A. Bokach, P. V. Gushchin, M. Haukka and V. Yu. Kukushkin, Dalton Trans., 2012, 41, 12857 DOI: 10.1039/C2DT30986F

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