Probing Ruthenium-Acetylide Bonding Interactions: Synthesis, Electrochemistry, and Spectroscopic Studies of Acetylide-Ruthenium Complexes Supported by Tetradentate Macrocyclic Amine and Diphosphine Li
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- 作者：Chun-Yuen Wong ; Chi-Ming Che ; Michael C. W. Chan ; Jie Han ; King-Hung Leung ; David Lee Phillips ; Kwok-Yin Wong ; and Nianyong Zhu
- 刊名：Journal of the American Chemical Society
- 出版年：2005
- 出版时间：October 12, 2005
- 年：2005
- 卷：127
- 期：40
- 页码：13997 - 14007
- 全文大小：247K
- 年卷期：v.127,no.40(October 12, 2005)
- ISSN：1520-5126
文摘
The synthesis and spectroscopic properties of trans-[RuL4(CMG SRC="/images/entities/tbd1.gif">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. Investigationsinto the effects of varying the [RuL4] core, acetylide ligands, and acetylide chain length for the[-C
mages/entities/tbd1.gif">C(C6H4Cmages/entities/tbd1.gif">C)n-1Ph] and [-Cmages/entities/tbd1.gif">C(C6H4)n-1Ph] (n = 1-3) series upon the electronic and electrochemicalcharacteristics of trans-[RuL4(Cmages/entities/tbd1.gif">CAr)2]0/+ are presented. DFT and TD-DFT calculations have beenperformed on trans-[Ru(L')4(Cmages/entities/tbd1.gif">CAr)2]0/+ (L' = PH3 and NH3) to examine the metal-acetylide mages/gifchars/pi.gif" BORDER=0 >-interactionand the nature of the associated electronic transition(s). It was observed that (1) the relationship betweenthe transition energy and 1/n for trans-[Ru(dmpe)2{Cmages/entities/tbd1.gif">C(C6H4Cmages/entities/tbd1.gif">C)n-1Ph}2] (n = 1-3) is linear, and (2)the sum of the dmages/gifchars/pi.gif" BORDER=0 >(RuII) mages/entities/rarr.gif"> mages/gifchars/pi.gif" BORDER=0 >*(Cmages/entities/tbd1.gif">CAr) MLCT energy for trans-[Ru(16-TMC or N2O2)(Cmages/entities/tbd1.gif">CAr)2] and the mages/gifchars/pi.gif" BORDER=0 >(Cmages/entities/tbd1.gif">CAr) mages/entities/rarr.gif"> dmages/gifchars/pi.gif" BORDER=0 >(RuIII) LMCT energy for trans-[Ru(16-TMC or N2O2)(Cmages/entities/tbd1.gif">CAr)2]+ corresponds to the intraligandmages/gifchars/pi.gif" BORDER=0 >mages/gifchars/pi.gif" BORDER=0 >* absorption energy for trans-[Ru(16-TMC or N2O2)(Cmages/entities/tbd1.gif">CAr)2]. The crystal structure of trans-[Ru(dmpe)2{Cmages/entities/tbd1.gif">C(C6H4Cmages/entities/tbd1.gif">C)2Ph}2] shows that the two edges of the molecule are separated by 41.7 Å. Theelectrochemical and spectroscopic properties of these complexes can be systematically tuned by modifyingL4 and Ar to give E1/2 values for oxidation of trans-[RuL4(Cmages/entities/tbd1.gif">CAr)2] that span over 870 mV and mages/gifchars/lambda.gif" BORDER=0 >max valuesof trans-[RuL4(Cmages/entities/tbd1.gif">CAr)2] that range from 19 230 to 31 750 cm-1. The overall experimental findings suggestthat the mages/gifchars/pi.gif" BORDER=0 >-back-bonding interaction in trans-[RuL4(Cmages/entities/tbd1.gif">CAr)2] is weak and the [RuL4] moiety in these moleculesmay be considered to be playing a "dopant" role in a linear rigid mages/gifchars/pi.gif" BORDER=0 >-conjugated rod.