Elsevier

Polyhedron

Volume 67, 8 January 2014, Pages 295-300
Polyhedron

Reactivity with aryldiazonium cations of hydrazine complexes of ruthenium and osmium

https://doi.org/10.1016/j.poly.2013.09.005Get rights and content

Abstract

The bis(amine) derivative [Os(NH3)2L4](BPh4)2 (1) formed when bis(hydrazine) complex [Os(NH2NH2)2L4](BPh4)2 was reacted with aryldiazonium salt [ArN2](BF4) in CH2Cl2 [L = P(OEt)3; Ar = 4-CH3C6H4]. Instead, reaction in (CH3)2CO afforded the bis(hydrazone) derivative [Os{NH2Ndouble bondC(CH3)2}2L4](BPh4)2 (2). The chloro-amine derivative [RuCl(NH3)L4](BPh4) (3) formed by reaction with [ArN2](BF4) in CH2Cl2 of complex [Ru(NH2NH2)2L4](BPh4)2, whereas amine-carbonyl derivative [Ru(NH3)(CO)L4](BPh4)2 (4) was obtained from [Ru(CO)(NH2NH2)L4](BPh4)2. Treatment of [Ru(NH2NH2)2L4](BPh4)2 with [ArN2](BF4) in (CH3)2CO afforded the bis(hydrazone) derivative [Ru{NH2Ndouble bondC(CH3)2}2L4](BPh4)2 (5). The complexes were characterised by IR and NMR spectroscopy and by X-ray crystal structure determination of complex 2.

Graphical abstract

The reaction of bis(hydrazine) complexes [M(NH2NH2)2L4](BPh4)2 (M = Ru, Os) with aryldiazonium salt affording bis(amine) [M(NH3)2L4](BPh4)2, chloro-amine [MCl(NH3)L4]BPh4, and bis(hydrazone) derivatives [M{NH2Ndouble bondC(CH3)2}2L4](BPh4)2 is described.

  1. Download : Download full-size image

Introduction

The chemistry of hydrazine complexes of transition metals has developed extensively in recent years [1], [2], mainly due to their close relationship with the dinitrogen fixation process [3], [4]. Many hydrazine complexes have thus been synthesised and several reactivity studies have been reported [1], [2]. Among the former, oxidation of coordinated NH2NH2 to give stable 1,2-diazene derivatives [M]–NHdouble bondNH [3] and reduction to ammonia are the most interesting [4], [5]. Deprotonation reactions with strong bases, affording both 1,2-diazene and dinitrogen derivatives [2], as well as the reaction with ketones yielding hydrazone derivatives, have also received attention [6]. However, although several reactivity studies have been reported, none of them concerns the reaction of coordinated hydrazine with aryldiazonium cations [ArN2]+.

We are interested in the chemistry of diazo complexes of transition metals and have reported the synthesis and reactivity of mono- and bis(hydrazine) complexes of the iron triad [7] of the type [M(CO)(NH2NH2)L4](BPh4)2 and [M(NH2NH2)2L4](BPh4)2 (L = phosphites). Oxidation with Pb(OAc)4 at low temperature of these complexes was extensively studied, affording new examples of mono- and bis(1,2-diazene) derivatives. We have now extended these studies to include reactivity with aryldiazonium salts of mono- and bis(hydrazine) complexes. This paper reports the results of these investigations.

Section snippets

General comments

All synthetic work was carried out in an appropriate atmosphere (Ar, N2) using standard Schlenk techniques or a vacuum atmosphere dry-box. All solvents were dried over appropriate drying agents, degassed on a vacuum line, and distilled into vacuum-tight storage flasks. RuCl3·3H2O and OsO4 were Pressure Chemical Co. (USA) products, used as received. Triethylphosphite P(OEt)3 was an Aldrich product, purified by distillation. Hydrazine NH2NH2 was prepared by decomposition of hydrazine cyanurate

Results and discussion

The bis(hydrazine) complex [Os(NH2NH2)2{P(OEt)3}4](BPh4)2 was reacted with aryldiazonium cations [ArN2]+ in CH2Cl2 to give the bis(amine) complex [Os(NH3)2{P(OEt)3}4](BPh4)2 (1) in about 80% yield (Scheme 1).

The formation of amine complex 1 was surprising, but can be explained as due to the reaction of the coordinate hydrazine with the aryldiazonium cation to give a tetrazene complex [A] (Scheme 2), which is probably unstable and decomposes, with loss of the arylazide molecule ArN3 and

Conclusions

Depending on both the nature of the solvent and the metal centre, the reaction of bis(hydrazine) complexes [M(NH2NH2)2L4](BPh4)2 (M = Ru, Os) with aryldiazonium salt affords bis(amine) [M(NH3)2L4](BPh4)2, chloro-amine [MCl(NH3)L4](BPh4), and bis(hydrazone) derivatives [M{NH2Ndouble bondC(CH3)2}2L4](BPh4)2.

Acknowledgment

We thank Mrs. Daniela Baldan, from the Università Ca’ Foscari Venezia, for her technical assistance.

References (20)

  • J.L. Crossland et al.

    Inorg. Chem.

    (2007)
    S. Dabb et al.

    Chem. Eur. J.

    (2008)
    L.D. Field et al.

    Inorg. Chem.

    (2009)
    L.D. Field et al.

    Inorg. Chem.

    (2010)
    L.D. Field et al.

    Inorg. Chem.

    (2011)
    J.L. Crossland et al.

    Inorg. Chem.

    (2012)
    L.D. Field et al.

    Inorg. Chem.

    (2013)
  • K.D. Demadis et al.

    Inorg. Chem.

    (1996)
    T.E. Glassman et al.

    J. Am. Chem. Soc.

    (1992)
  • D. Sutton

    Chem. Rev.

    (1993)
    H. Kisch et al.

    Adv. Organomet. Chem.

    (1992)
    H. Zollinger

    Diazo Chemistry II

    (1995)
    B.F.G. Johnson et al.B.T. Heaton et al.

    Coord. Chem. Rev.

    (1996)
  • D. Sellmann et al.

    Angew. Chem., Int. Ed. Engl.

    (1989)
    D. Sellmann et al.

    Inorg. Chem.

    (1993)
    M.R. Smith et al.

    J. Am. Chem. Soc.

    (1993)
    T.-Y. Cheng et al.

    J. Am. Chem. Soc.

    (1994)
    G. Albertin et al.

    Inorg. Chem.

    (1997)
    D. Sellmann et al.

    Eur. J. Inorg. Chem.

    (2000)
  • M. Hidai et al.

    Chem. Rev.

    (1995)
    D. Sellmann et al.

    Acc. Chem. Res.

    (1997)
    M.D. Fryzuk et al.

    Coord. Chem. Rev.

    (2000)
    S.M. Malinak et al.

    Prog. Inorg. Chem.

    (2001)
    B.A. MacKay et al.

    Chem. Rev.

    (2004)
    J.B. Howard et al.

    Chem. Rev.

    (1996)
    B.K. Burgess et al.

    Chem. Rev.

    (1996)
    R.Y. Igarashi et al.

    Crit. Rev. Biochem. Mol. Biol.

    (2003)
    B.M. Barney et al.

    Dalton Trans.

    (2006)
    J.L. Crossland et al.

    Coord. Chem. Rev.

    (2010)
  • M.J. Nolte et al.

    J. Chem. Soc., Dalton Trans.

    (1974)
    E. Singleton et al.

    Inorg. Chim. Acta

    (1982)
  • G. Albertin et al.

    Inorg. Chem.

    (1998)
    G. Albertin et al.

    J. Chem. Soc., Dalton Trans.

    (1997)
    G. Albertin et al.

    J. Chem. Soc., Dalton Trans.

    (1997)
    G. Albertin et al.

    Inorg. Chem. Commun.

    (2001)
    G. Albertin et al.

    Inorg. Chem.

    (2005)
  • E. Nachbaur et al.

    Monatsh. Chem.

    (1971)
  • A.I. Vogel

    Practical Organic Chemistry

    (1956)
  • G. Balacco,...
There are more references available in the full text version of this article.

Cited by (0)

View full text