Phenylene as an efficient mediator for intermetallic electronic coupling

Abstract

The new compound [(NC)Ru2(ap)4]2(μ-1,4-C6H4) (ap = 2-anilinopyridinate) was prepared to address the open question of whether a 1,4-phenylene bridge can mediate intermetallic electronic coupling. As a manifestation of strong coupling,...

Enabling Valence Delocalization in Iron(III) Macrocyclic Complexes through Ring Unsaturation

“…62 and 53%, respectively, of the predicted values. These fall within the range associated with recent species assigned as either valence-trapped with very strong coupling (Robin-Day class II–III) ,, or completely valence-delocalized (Robin-Day class III). − The moderate solvatochromism of 3b 2+ , ,, and the two separate ν­(CC) bands in the IR spectrum of 3c 2+ preclude a completely valence-delocalized description. , Therefore, 3b / c 2+ are conservatively assigned as valence-trapped complexes exhibiting moderate ( 3c 2+ ) to strong ( 3b 2+ ) coupling (Robin-Day class II, perhaps approaching class II–III). For 3a 2+ , similar behavior to 3b 2+ is likely based both on the similar intensity of the IVCT bands (Table ) and on the apparent valence delocalization of 3a 2+ on the IR timescale.…”

Influence of Changing the Remote Substituents on Charge Transfer Properties of Cyanide‐Bridged Trinuclear Fe−Ru−Fe Complexes

“…The IR spectrum of cyanido‐bridged complexes has a characteristic CN stretching vibration [17] . With the change of the oxidation state of the iron center of the compounds, the CN stretching vibration frequency (ν CN ) is shifted correspondingly.…”

“…The IR spectrum of cyanido-bridged complexes has a characteristic CN stretching vibration. [17] With the change of the oxidation state of the iron center of the compounds, the 1, 2, 3 and n = 2, 3, 4) in KBr. 1[PF 6 ] 2 and 2075 cm À 1 for trans-(dmptpy)Ru(PPh 3 )(CN) 2 ) that corresponded to an anti-symmetrical mode of CN stretching vibration, and the ν CN of 1[PF 6 ] 2 is significantly increased relative to trans-(dmptpy)Ru(PPh 3 )(CN) 2 , which is consistent with the trend of the similar compounds. [12,18] For the one-electron oxidation product 1[PF 6 ] 3 , two CN signals appear, corresponding to the symmetrical mode (2084 cm À 1 ) and anti-symmetrical mode (2038 cm À 1 ) of CN stretching vibration, which are common in similar mixed valence complexes.…”

Bisaryl and Bisalkynyl Diruthenium (III,III) Compounds Based on an Electron-Deficient Building Block

“…Many examples of Ru 2 organometallic compounds have been disclosed since the seminal report of Ru 2 ( ap ) 4 (C 2 Ph) ( ap = 2-anilinopyridinate) by Cotton and Chakravarty and subsequent studies by Bear and Kadish. , Ru 2 ( ap ) 4 -based compounds are highly robust both under ambient conditions and over a broad electrochemical window, and spectroelectrochemistry studies of the Ru 2 ( ap )-bridge-Ru 2 ( ap ) type compounds have provided clear evidence for facile charge delocalization across oligoynyl (bridge = C 2n ) − and aryl (bridge = C 6 H 4 ) bridges . The chemical robustness of Ru 2 ( ap ) 4 -based compounds also allows for iterative on-complex Cadiot–Chodkiewicz coupling, yielding extended oligo-yne compounds Ru 2 ( ap ) 4 (C 2 k SiR 3 ) with k up to 5 .…”

“…17,18 Ru 2 (ap) 4 -based compounds are highly robust both under ambient conditions and over a broad electrochemical window, and spectroelectrochemistry studies of the Ru 2 (ap)-bridge-Ru 2 (ap) type compounds have provided clear evidence for facile charge delocalization across oligoynyl (bridge = C 2n ) 19−22 and aryl (bridge = C 6 H 4 ) bridges. 23 The chemical robustness of Ru 2 (ap) 4 -based compounds also allows for iterative oncomplex Cadiot−Chodkiewicz coupling, yielding extended oligo-yne compounds Ru 2 (ap) 4 (C 2k SiR 3 ) with k up to 5. 24 The ability to mediate charge transfer has been exploited in the construct of prototypical molecular wires 25 and devices.…”