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Spectroscopic Studies and Structures oftrans-Ruthenium(II) and Ruthenium(III) Bis(cyanide) Complexes Supported by a Tetradentate Macrocyclic Tertiary Amine Ligand

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Title: Spectroscopic Studies and Structures oftrans-Ruthenium(II) and Ruthenium(III) Bis(cyanide) Complexes Supported by a Tetradentate Macrocyclic Tertiary Amine Ligand
Authors: Yung, FC, Zhu, N, Che, CM, Wong, CY, Lee, FW, Phillips, DL
Source: Inorganic Chemistry. 47:10308-10316
Publisher Information: American Chemical Society (ACS), 2008.
Publication Year: 2008
Subject Terms: Macrocyclic Compounds, Organometallic Compounds - Chemical Synthesis - Chemistry, 02 engineering and technology, Crystallography, X-Ray, Ligands, Spectrum Analysis, Raman, 01 natural sciences, Ruthenium, Macrocyclic Compounds - Chemical Synthesis - Chemistry, Electrochemistry, Organometallic Compounds, Amines, Raman, Ultraviolet, Crystallography, Cyanides, Spectrum Analysis, Amines - Chemical Synthesis - Chemistry, 0104 chemical sciences, Spectrophotometry, X-Ray, Cyanides - Chemical Synthesis - Chemistry, Spectrophotometry, Ultraviolet, 0210 nano-technology, Ruthenium - Chemistry
Description: trans-[Ru(16-TMC)(C[triple bond]N)2] (1; 16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) was prepared by the reaction of trans-[Ru(16-TMC)Cl2]Cl with KCN in the presence of zinc powder. The oxidation of 1 with bromine gave trans-[Ru(16-TMC)(CN)2]+ isolated as PF6 salt (2.PF6). The Ru-C/C-N distances are 2.061(4)/1.130(5) and 2.069(5)/1.140(7) A for 1 and 2, respectively. Both complexes show a Ru(III/II) couple at 0.10 V versus FeCp2+/0. The UV-vis absorption spectrum of 1 is dominated by an intense high-energy absorption at lambda(max) = 230 nm, which is mainly originated from dpi(RuII) --> pi*(N[triple bond]C-Ru-C[triple bond]N) charge-transfer transition. Complex 2 shows intense absorption bands at lambda(max) pi*(N[triple bond]C-Ru-C[triple bond]N) and sigma(-CN) --> d(RuIII) charge-transfer transition, respectively. Density functional theory and time-dependent density-functional theory calculations have been performed on trans-[(NH3)4Ru(C[triple bond]N)2] (1') and trans-[(NH3)4Ru(C[triple bond]N)2]+ (2') to examine the Ru-cyanide interaction and the nature of associated electronic transition(s). The 230 nm band of 1 has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal nuC[triple bond]N stretch mode accounts for ca. 66% of the total vibrational reorganization energy. A change of nominal bond order for the cyanide ligand from 3 to 2.5 is estimated upon the electronic excitation.
Document Type: Article
Language: English
ISSN: 1520-510X
0020-1669
DOI: 10.1021/ic800743a
Access URL: https://pubmed.ncbi.nlm.nih.gov/18850698
https://www.ncbi.nlm.nih.gov/pubmed/18850698
https://pubs.acs.org/doi/10.1021/ic800743a
http://hub.hku.hk/handle/10722/168346
https://core.ac.uk/display/37992551
https://pubs.acs.org/doi/abs/10.1021/ic800743a
http://www.crystallography.net/cod/4305799.html
http://hdl.handle.net/10722/168346
Accession Number: edsair.doi.dedup.....062e37f87d1d802e91a6a1dbf8bc57aa
Database: OpenAIRE
Description
Abstract:trans-[Ru(16-TMC)(C[triple bond]N)2] (1; 16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) was prepared by the reaction of trans-[Ru(16-TMC)Cl2]Cl with KCN in the presence of zinc powder. The oxidation of 1 with bromine gave trans-[Ru(16-TMC)(CN)2]+ isolated as PF6 salt (2.PF6). The Ru-C/C-N distances are 2.061(4)/1.130(5) and 2.069(5)/1.140(7) A for 1 and 2, respectively. Both complexes show a Ru(III/II) couple at 0.10 V versus FeCp2+/0. The UV-vis absorption spectrum of 1 is dominated by an intense high-energy absorption at lambda(max) = 230 nm, which is mainly originated from dpi(RuII) --> pi*(N[triple bond]C-Ru-C[triple bond]N) charge-transfer transition. Complex 2 shows intense absorption bands at lambda(max) pi*(N[triple bond]C-Ru-C[triple bond]N) and sigma(-CN) --> d(RuIII) charge-transfer transition, respectively. Density functional theory and time-dependent density-functional theory calculations have been performed on trans-[(NH3)4Ru(C[triple bond]N)2] (1') and trans-[(NH3)4Ru(C[triple bond]N)2]+ (2') to examine the Ru-cyanide interaction and the nature of associated electronic transition(s). The 230 nm band of 1 has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal nuC[triple bond]N stretch mode accounts for ca. 66% of the total vibrational reorganization energy. A change of nominal bond order for the cyanide ligand from 3 to 2.5 is estimated upon the electronic excitation.
ISSN:1520510X
00201669
DOI:10.1021/ic800743a