Jump to main content
Jump to site search

Issue 40, 2016
Previous Article Next Article

Synthesis and characterization of five-coordinate, 16-electron RuII complexes supported by tridentate bis(phosphino)silyl ligation

Author affiliations

Abstract

The synthesis of 16-electron complexes of the type (Cy-PSiP)RuX(L) (Cy-PSiP = κ3-(2-Cy2PC6H4)2SiMe) is reported. Treatment of (Cy-PSiP)H with one equiv. RuCl2(PPh3)3 in the presence of Et3N afforded a mixture of (Cy-PSiP)RuCl(PPh3) (1) and [(Cy-PSiP)RuCl]2 (2), which exists in a temperature-dependent equilibrium process involving reversible dissociation of PPh3 from 1 to form 2. While treatment of this equilibrium mixture with PMe3 afforded (Cy-PSiP)RuCl(PMe3) (3) cleanly, this product was more straightforwardly prepared by the addition of PMe3 to 2 (97% yield). Attempts to form an alkyl complex of the type (Cy-PSiP)RuMe(PMe3) via treatment of 3 with MeMgBr led to the dehydrogenation and cyclometalation of a cyclohexyl phosphino group to give the isolable 18-electron complex [MeSi(C6H4PCy2)(C6H4PCy(η3-C6H8))]RuPMe3 (4, 78% yield). The hydrido complex (Cy-PSiP)RuH(PMe3) (5) was identified as a minor by-product in this dehydrogenative process. Whereas simple 16-electron alkyl complexes of the type (Cy-PSiP)RuR(PMe3) remained elusive, the isolable allyl complex (Cy-PSiP)Ru(η3-C3H5) (9) was successfully prepared from 2 and (C3H5)MgCl (79% yield). Treatment of 3 with Me3SiN3 or NaN3 did not generate a five-coordinate azido species. However, the putative dinuclear complex [(Cy-PSiP)RuN3]2 (10) was observed to react with one equiv. of PMe3 to afford the isolable five-coordinate azido complex (Cy-PSiP)Ru(N3)(PMe3) (11; 94% yield). Crystallographic data for 3, 4, 5, 9 and 11 are presented.

Graphical abstract: Synthesis and characterization of five-coordinate, 16-electron RuII complexes supported by tridentate bis(phosphino)silyl ligation

Back to tab navigation

Supplementary files

Publication details

The article was received on 11 May 2016, accepted on 27 May 2016 and first published on 07 Jun 2016


Article type: Paper
DOI: 10.1039/C6DT01869F
Citation: Dalton Trans., 2016,45, 15850-15858

  •   Request permissions

    Synthesis and characterization of five-coordinate, 16-electron RuII complexes supported by tridentate bis(phosphino)silyl ligation

    M. C. MacInnis, A. J. Ruddy, R. McDonald, M. J. Ferguson and L. Turculet, Dalton Trans., 2016, 45, 15850
    DOI: 10.1039/C6DT01869F

Search articles by author

Spotlight

Advertisements