Synthesis and characterization of five-coordinate, 16-electron RuII complexes supported by tridentate bis(phosphino)silyl ligation. Issue 40 (7th June 2016)

• Record Type: Journal Article
• Authors: MacInnis, Morgan C.; Ruddy, Adam J.; McDonald, Robert; Ferguson, Michael J.; Turculet, Laura
• Is Part Of: Dalton transactions. Volume 45:Issue 40(2016)
• Page Start: 15850
• Page End: 15858
• Publication Date: 2016-06-07
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt01869f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : New electronically and coordinatively unsaturated complexes of the type (Cy-PSiP)RuX(L) (Cy-PSiP = κ 3 -(2-Cy2 P C6 H4 )2 Si Me) are reported, including examples of 16-electron allyl and azido Ru species. Abstract : The synthesis of 16-electron complexes of the type (Cy-PSiP)RuX(L) (Cy-PSiP = κ 3 -(2-Cy2 P C6 H4 )2 Si Me) is reported. Treatment of (Cy-PSiP)H with one equiv. RuCl2 (PPh3 )3 in the presence of Et3 N 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 from1 to form2 . 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 to2 (97% yield). Attempts to form an alkyl complex of the type (Cy-PSiP)RuMe(PMe3 ) via treatment of3 with MeMgBr led to the dehydrogenation and cyclometalation of a cyclohexyl phosphino group to give the isolable 18-electron complex [MeSi(C6 H4 PCy2 )(C6 H4 PCy(η 3 -C6 H8 ))]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(η 3 -C3 H5 ) (9 ) was successfully prepared from2 and (C3 H5 )MgCl (79% yield). Treatment of3 with Me3 SiN3 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 for3, 4, 5, 9 and11 are presented.