- Phenylchromium(III) Chemistry Revisited 100 Years after Franz Hein (Part II): From LinCrPh3+ n(thf)x(n = 1, 2, 3) to Dimeric Triphenylchromate(II) Complexes
-
Polyphenylchromium(III) organometallics with various phenylation degrees and stabilized by diverse Lewis bases with various donor strengths and denticity were investigated in order to better understand the formation of (η6-arene)chromium complexes according to the procedure of Franz Hein (1892-1976) [ Organometallics 2019, 38, 498-511, DOI: 10.1021/acs.organomet.8b00811]. Part II focuses on hexa-, penta-, and tetraphenylchromates(III). Chromium(III) compounds with a lower phenylation degree will be discussed in a future part III. The numbering scheme of the complexes relates to the number of Cr-bound phenyl substituents. Hexaphenylchromate(III): The reaction of Ph3Cr(thf)3·0.25dx (3) (dx = 1,4-dioxane) with an ethereal solution of phenyllithium yields yellow-orange [Li3CrPh6(thf)2.3(OEt2)0.7] (6-thf-OEt2) which slowly degrades in contact with the reaction solution leading to emerald-green crystals of [{(Et2O)Li}2Ph3Cr(μ-O)]2 (3-Li2O). Pentaphenylchromate(III): Compound 6-thf-OEt2 reacts with 1 equiv of HCl-OEt2 solution to turquoise [{(thf)2Li}{(Et2O)Li}CrPh5] (5-thf-OEt2) that reacts with THF to the green contact ion pair [{(thf)2Li}2CrPh5] (5-thf) and with 12-crown-4 (12C4) to the light green solvent-separated ion pair [(12C4)Li(thf)]2 [CrPh5] (5-thf-12C4). Refluxing of 5-thf-OEt2 in diethyl ether leads to ether degradation and formation of 3-Li2O, whereas 5-thf-12C4 liberates biphenyl under similar reaction conditions. Tetraphenylchromate(III): The reaction of 3 with 1 equiv of phenyllithium in THF leads to a green reaction mixture. At -50 °C, red [(thf)4Li] [cis-(thf)2CrPh4]·2THF (4-thf) crystallizes which reversibly transforms into a green oil above -50 °C. Upon acidolysis of 5-thf-OEt2 with 1 equiv of HCl-OEt2 at -20 °C, the intermediately formed red complex is reduced to the dinuclear chromate(II) [{(thf)Li}CrPh3]2 (3-CrII-thf) (Cr-Cr 187.66(8) pm). Recrystallization of this product from THF yields solvent-separated [(thf)4Li]2 [(CrPh3)2] (3-CrII-thf4) with a Cr-Cr quadruple bond (Cr-Cr 183.7(2) pm) without contacts between the lithium ions and Cr-bound phenyl groups. Complex 3-CrII-thf reacts at room temperature in diethyl ether to the sandwich complexes bis(biphenyl)chromium(0) [(η6-Ph2)2Cr0] (π-4) and benzene-biphenylchromium(0) [(η6-C6H6)(η6-Ph2)Cr0] (π-3). Compounds in bold letters are authenticated by X-ray structure determinations.
- Fischer, Reinald,G?rls, Helmar,Suxdorf, Regina,Westerhausen, Matthias
-
p. 3892 - 3905
(2020/11/13)
-
- DFT-Supported Threshold Ionization Study of Chromium Biphenyl Complexes: Unveiling the Mechanisms of Substituent Influence on Redox Properties of Sandwich Compounds
-
High-resolution mass-analyzed threshold ionization (MATI) spectra of (η6-Ph2)2Cr and (η6-Ph2)(η6-PhMe)Cr demonstrate that the Ph groups work as electron donors, decreasing the ionization energy of the gas-phase bisarene complexes. In contrast to electrochemical data, a close similarity of the Ph and Me group effects on the oxidation of free sandwich molecules has been revealed. However, DFT calculations testify for the opposite shifts of the electron density caused by the Me and Ph substituents in the neutral complexes, the latter behaving as an electron-accepting fragment. On the contrary, in the bisarene cations, the Ph group becomes a stronger donor than methyl. This change provides the similar substituent effects observed with the MATI experiment. On the other hand, the well-documented opposite influence of the Me and Ph fragments on the redox potential of the (η6-arene)2Cr+/0 couple in solution appears to be a result of solvation effects but not intramolecular interactions as shown for the first time in this work.
- Ketkov, Sergey Yu.,Tzeng, Sheng-Yuan,Wu, Pei-Ying,Markin, Gennady V.,Tzeng, Wen-Bih
-
p. 13669 - 13675
(2017/10/09)
-
- Organometallic chemistry of the transition elements. 5. An improved synthetic route to (arene)chromium π-complexes
-
A new, solvent-free synthetic route to bis(η6-arene)chromium(0) compounds incorporating ligands with low vapor pressures is discussed. The direct reaction of chromium metal atoms with both model ligands (durene, pentamethylbenzene, and hexamethylbenzene) and ligands containing two sites at which π-complexation to metal atoms can occur (biphenyl, diphenylmethane, and trans-stilbene) is described. The preparation and characterization of several of the resulting compounds are reported for the first time via the direct metal atom synthesis technique.
- Markle, Richard J.,Pettijohn, Ted M.,Lagowski
-
p. 1529 - 1531
(2008/10/08)
-