SciELO - Scientific Electronic Library Online

 
vol.62 índice de autoresíndice de assuntospesquisa de artigos
Home Pagelista alfabética de periódicos  

Serviços Personalizados

Artigo

Indicadores

Links relacionados

  • Em processo de indexaçãoCitado por Google
  • Em processo de indexaçãoSimilares em Google

Compartilhar


South African Journal of Chemistry

versão On-line ISSN 1996-840X
versão impressa ISSN 0379-4350

S.Afr.j.chem. (Online) vol.62  Durban  2009

 

RESEARCH ARTICLE

 

Solventless substitution reaction of solid phosphine ligands with Ru(C5H4R)(CO)2I (R = H, Me)

 

 

Apollinaire Munyaneza; Muhammad D. Bala; Neil J. Coville

Molecular Sciences Institute and School of Chemistry, University of the Witwatersrand, Johannesburg 2050, South Africa

 

 


ABSTRACT

The solventless reaction between Ru(C5H4R)(CO)2I (R = H, Me) and solid phosphine ligands [PPh3/ P(p-MeOC6H4)3, P(m-MeC6H4)3,P(p-FC6H4)3,P(p-ClC6H4)3] was undertaken at various temperatures with all the reactions occurring in the melt phase. The reaction rates and type of products isolated are dependent on the electronic properties of the Cp-substituent and the para-substituent on the phosphine ligands. For the C5H4R moiety, when R = H the ligand substitution product Ru(C5H5)(CO)(PR3) I was obtained, and the ligand addition product [Ru(C5H4Me)(CO)2(PR3)]I was predominantly obtained when R = Me. The reaction rates are enhanced by para-substituted electron-donating phosphines. These results are similar to those obtained from studies utilizing benzene and xylene as solvents. The products have been characterized by FTIR and NMR spectroscopy and by MS. The complex Fe2(C5H5)2(CO)4 was found to act as a catalyst in all the melt reactions.

Keyword: Solvent-free, ruthenium, cyclopentadienyl complexes, phosphines


 

 

Full text available only in PDF format.

 

Acknowledgements

We thank the NRF, THRIP and the University of the Witwaters-rand for financial support. We are grateful to Impala Platinum for a loan of ruthenium compounds.

 

References

1 J. Lin, P. Gao, B. Li, S. Xu, H. Song and B. Wang, Inorg. Chim. Acta, 2006, 359, 4503-4510.         [ Links ]

2 M. Di Vaira, M. Peruzzini, S.S. Costantini and P. Stoppioni, J. Organomet. Chem., 2006, 691, 3931-3937.         [ Links ]

3 B. Demerseman, J.L. Renaud, L. Toupet, C. Hubert and C. Bruneau, Eur. J. Inorg. Chem., 2006, 7, 1371-1380.         [ Links ]

4 G. Wilkinson, F.G.A. Stone and E.W. Abel, eds., Comprehensive Organometallic Chemistry, vol. 7, Pergamon Press, Oxford, UK, 1995, pp. 476-527.         [ Links ]

5 P. Govindaswamy, Y.A. Mozharivskyj and M.R. Kollipara, Polyhedron, 2004, 23, 1567-1572.         [ Links ]

6 C.A. Mebi, R.P. Nair andB.J. Frost, Organometallics, 2007, 26, 429-438.         [ Links ]

7 N.J. Coville and E.A. Darling, J. Organomet. Chem., 1984, 277, 105-111.         [ Links ]

8 J.C.A. Boeyens, N.J. Coville and K. Soldenhoff, S. Afr. J. Chem., 1984, 37, 153-160.         [ Links ]

9 D.A. Brown, H.J. Lyons and R.T. Sane, Inorg. Chim. Acta, 1970, 4, 621-625.         [ Links ]

10 J.M.Smith,S.C.PellyandN.J.Coville, J. Organomet. Chem., 1996, 525, 159-166.         [ Links ]

11 A. Munyaneza, M.D. Bala and N.J. Coville, Z. Naturforsch, 2007, 62b, 453-459.         [ Links ]

12 C. White and R.J. Mawby, Inorg. Chim. Acta, 1970, 4, 261-266.         [ Links ]

13 D.A. Brown, H.J. Lyons, A.R. Manning and J.M. Rowley, Inorg. Chim. Acta, 1969, 3, 346-350.         [ Links ]

14 R.J. Haines, A.L. Du Preez and I.L. Marais, J. Organomet. Chem., 1971, 28, 405-413.         [ Links ]

15 P.M. Treichel, R.L. Shubkin, K.W Barnett and D. Reichard, Inorg. Chem., 1966, 5, 1177-1181.         [ Links ]

16 M.E. Rerek and F. Basolo, Organometallics, 1983, 2, 372-376.         [ Links ]

17 H.G. Schuster-Woldan and F. Basolo, J. Am. Chem. Soc., 1966, 88, 1657-1663.         [ Links ]

18 K. Tabatabaian and C. White, Inorg. Chem., 1981, 20, 2020-2022.         [ Links ]

19 M.S. Loonat, Substituted-Cyclopentadienyl Half-Sandwich Group 6 and Group 8 Transition Metal Complexes, Ph.D. thesis, University of the Witwatersrand, Johannesburg, South Africa, 1989, pp. 136-150.         [ Links ]

20 I.C. Paul and D.Y. Curtin, Acc. Chem. Res., 1973, 6, 217-225.         [ Links ]

21 G.W.V. Cave, C.L. Raston and J.L. Scott, Chem. Commun., 2001, 2159-2169.         [ Links ]

22 A.L. Garay, A. Pichon and S.L. James, Chem. Soc. Rev., 2007, 36, 846-855.         [ Links ]

23 S.L. Gipson, L.-K. Liu and R.U. Soliz, J. Organomet. Chem., 1996, 526, 393-395.         [ Links ]

24 T. Blackmore, M.I. Bruce and F.G.A. Stone, J. Chem. Soc., A, 1968, 2158-2162.         [ Links ]

25 O.G. Adeyemi and N.J. Coville, Organometallics, 2003, 22, 2284-2290.         [ Links ]

26 R. Bogadi, D.C. Levendis and N.J. Coville, J. Am. Chem. Soc, 2002, 124, 1104-1110.         [ Links ]

 

 

Received 2 June 2008
Revised 6 November 2008
Accepted 11 December 2008

 

 

* Present address: School of Chemistry, University of KwaZulu-Natal, Private Bag X54001, Westville Campus, Durban 4000, South Africa.
** To whom correspondence should be addressed.E-mail: neil.coville@chem.wits.ac.za

Creative Commons License Todo o conteúdo deste periódico, exceto onde está identificado, está licenciado sob uma Licença Creative Commons