Please use this identifier to cite or link to this item:
Title: Probing ruthenium-acetylide bonding interactions : synthesis, electrochemistry, and spectroscopic studies of acetylide-ruthenium complexes supported by tetradentate macrocyclic amine and diphosphine ligands
Authors: Wong, CY
Che, CM
Chan, MCW
Han, J
Leung, KH
Phillips, DL
Wong, KY 
Zhu, N
Issue Date: 2005
Source: Journal of the American Chemical Society, 2005, v. 127, no. 40, p. 13997-14007 How to cite?
Journal: Journal of the American Chemical Society 
Abstract: The synthesis and spectroscopic properties of trans-[RuL 4(C≡CAr)2] (L4 = two 1,2-bis- (dimethylphosphino)ethane, (dmpe)2; 1,5,9,13-tetramethyl-1,5,9,13- tetraazacyclohexadecane, 16-TMC; 1,-12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8- dioxacyclopentadecane, N2O2) are described. Investigations into the effects of varying the [RuL4] core, acetylide ligands, and acetylide chain length for the [-C≡C(C6H 4C=C)n-1Ph] and [-C≡C(C6H 4)n-1Ph] (n = 1-3) series upon the electronic and electrochemical characteristics of trans-[RuL4(C≡CAr) 2]0/+ are presented. DFT and TD-DFT calculations have been performed on frans-[Ru(L′)4(C≡CAr)2] 0/+ (L′ = PH3 and NH3) to examine the metal-acetylide π-interaction and the nature of the associated electronic transition(s). It was observed that (1) the relationship between the transition energy and 1/n for trans-[Ru(dmpe)2{C≡C(C6H 4C≡C)n-1Ph}2] (n = 1-3) is linear, and (2) the sum of the dπRuII) → π*(C≡CAr) MLCT energy for trans-[Ru(16-TMC or N2O2)(C≡CAr) 2] and the π-(C≡CAr) → dπ(RuIII) LMCT energy for trans-[Ru(16-TMC or N2O2)(C≡CAr) 2]+ corresponds to the intraligand ππ* absorption energy for trans-[Ru(16-TMC or N2O2) (C≡CAr)2]. The crystal structure of trans-[Ru(dmpe) 2-{C≡C(C6H4C≡C)2Ph} 2] shows that the two edges of the molecule are separated by 41.7 Å. The electrochemical and spectroscopic properties of these complexes can be systematically tuned by modifying L4 and Ar to give E 1/2 values for oxidation of trans-[RuL4(C≡CAr) 2] that span over 870 mV and λmax values of trans-[RuL4(C≡CAr)2] that range from 19 230 to 31 750 cm-1. The overall experimental findings suggest that the π-back-bonding interaction in trans-[RuL4(C≡CAr) 2] is weak and the [RuL4] moiety in these molecules may be considered to be playing a "dopant" role in a linear rigid π-conjugated rod.
ISSN: 0002-7863
DOI: 10.1021/ja053076+
Appears in Collections:Journal/Magazine Article

View full-text via PolyU eLinks SFX Query
Show full item record


Last Week
Last month
Citations as of Oct 20, 2018


Last Week
Last month
Citations as of Oct 18, 2018

Page view(s)

Last Week
Last month
Citations as of Oct 15, 2018

Google ScholarTM



Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.