Issue 8, 2000
From the journal:

Journal of the Chemical Society, Dalton Transactions

Unusual pathways for the reaction between [MCl2(Me2SO)4] (M = Os, Ru) and hydrazine dihydrochloride: deoxygenation of sulfoxidesvs. coordination of hydrazinium

M. Fátima C. Guedes da Silva,b   Armando J. L. Pombeiro,*a   Silvano Geremia,c   Ennio Zangrando,c   Mario Calligaris,*c   Andrey V. Zinchenkod  and  Vadim Yu. Kukushkin*e  

* Corresponding authors

a Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais, Lisbon, Portugal
E-mail: pombeiro@alfa.ist.utl.pt

b Universidade Lusófona de Humanidades e Tecnologias, Av. Campo Grande 376, Lisbon, Portugal

c Dipartimento di Scienze Chimiche, University of Trieste, via L. Giorgieri 1, Italy
E-mail: calligaris@univ.trieste.it

d Inorganic Chemistry, St. Petersburg State Technological Institute, Zagorodny Pr. 49, St. Petersburg, Russian Federation

e Department of Chemistry, St. Petersburg State University, Stary Petergof, Russian Federation
E-mail: kukushkin@VK2100.spb.edu

Abstract

Reaction of trans-[OsCl2(Me2SO)4] 1 with excess N2H4·2HCl leads to the osmium(III) compound mer-[OsCl3(NH3)2(Me2S)] 2 in the course of concerted reactions, i.e. oxidation of the metal, deoxygenation of the sulfoxide, disproportionation of hydrazine and substitution by NH3. In contrast, interaction of cis-[RuCl2(Me2SO)4] cis-3 with hydrazine dihydrochloride brings about easy substitution (without redox conversion) leading to mer-[RuCl3(N2H5)(Me2SO)2] 4 which is a rare example of a hydrazinium complex. X-Ray single-crystal diffraction analyses were performed on 1, 2 and 4. In 4, one Ru–S bond is unusually short due to the enhanced π bonding contribution as a result of an intramolecular H-bond between the Me2SO and the cis N2H5+ group. The complexes show anodic oxidations and 4, that in aqueous medium undergoes spontaneous dehydrochlorination, exhibits by controlled potential electrolysis a multi-electron oxidation process with anodically-induced H+ loss, oxidation of the hydrazine ligand to N2 and N-oxides, and of Me2SO to SO2. The anodic waves of Me2SO or H2O solutions of cis-3 were assigned to trans-[RuCl2(Me2SO-S )4] trans-3 and [RuCl(H2O)2(Me2SO-S )3]+, respectively. The oxidation potential values were interpreted on the basis of redox potential–structure relationships and the Lever electrochemical parameter EL was tentatively estimated for both S- and O-coordinated Me2SO and for the hydrazinium ligand, showing that Me2SO-S in our complexes behaves as a significant π-electron acceptor and N2H5+ as a rather weak net electron donor, and applied to predict the oxidation potential of some Ru and Os complexes.

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Article information

DOI
https://doi.org/10.1039/A908170D
Article type
Paper
Submitted
12 Oct 1999
Accepted
03 Mar 2000
First published
31 Mar 2000

J. Chem. Soc., Dalton Trans., 2000, 1363-1371

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Unusual pathways for the reaction between [MCl2(Me2SO)4] (M = Os, Ru) and hydrazine dihydrochloride: deoxygenation of sulfoxides vs. coordination of hydrazinium

M. F. C. Guedes da Silva, A. J. L. Pombeiro, S. Geremia, E. Zangrando, M. Calligaris, A. V. Zinchenko and V. Yu. Kukushkin, J. Chem. Soc., Dalton Trans., 2000, 1363 DOI: 10.1039/A908170D

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