Syntheses, Structures, and Spectro-electrochemistry of {Cp*(PP)Ru}C≡CC≡C{Ru(PP)Cp*} (PP = dppm, dppe) and Their Mono- and Dications

Bruce, M.I.; Ellis, B.G.; Low, P.J.; Skelton, B.W.; White, A.H.

Abstract

The complexes {Cp*(PP)Ru}(2)(mu-Cequivalent toCCequivalent toC) (PP = dppm 5a, dppe 5b) have been synthesized from RuCl(PP)Cp* (1a/b) via the corresponding vinylidenes [Ru(=C=CH2)(PP)Cp*](+) (2a/b), deprotonation (KOBut) to the ethynyls Ru(Cequivalent toCH)(PP)Cp* (3a/b), oxidative coupling ([FeCp2][PF6]) to the bis(vinylidenes) [{Ru(PP)Cp*}2{mu-(=C=CHCH=C=)}](2+) (4a/b), and deprotonation [dbu (4a), KOBut (4b)]. Electrochemistry of 5a/b revealed the expected sequence of four le redox steps, which occurred at significantly lower Edegrees values than found for the Ru(PPh3)(2)Cp analogue. Single-crystal X-ray structure determinations are reported for 1a/b, 2a/b, 3a/b, 4a/b, and 5a/b, together with the oxidized products [5b] [PF6](n) (n = 1, 2). In the monocation [5b] [PF6] the Ru-C(l) [1.931(2) Angstrom] and C-C distances [1.248-1.338(3) Angstrom] are intermediate between those found in 5b and the dication [5b](2+). The short Ru-C [1.857(5) Angstrom] and experimentally equal C-C distances [1.269-1.280(6) Angstrom] in [5b] [PF6](2) confirm the anticipated dicarbene-cumulene structure for the Ru=C=C=C=C=Ru bridge.

Citation

Bruce, M., Ellis, B., Low, P., Skelton, B., & White, A. (2003). Syntheses, Structures, and Spectro-electrochemistry of {Cp*(PP)Ru}C≡CC≡C{Ru(PP)Cp*} (PP = dppm, dppe) and Their Mono- and Dications. Organometallics, 22(16), 3184-3198. https://doi.org/10.1021/om030015g

• Journal Article Type: Article
• Publication Date: 2003-08
• Deposit Date: Apr 20, 2007
• Journal: Organometallics
• Print ISSN: 0276-7333
• Electronic ISSN: 1520-6041
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 22
• Issue: 16
• Pages: 3184-3198
• DOI: https://doi.org/10.1021/om030015g
• Public URL: https://durham-repository.worktribe.com/output/1571232