Rare-earth metal ethylene and ethyne complexes
Wen Jiang1, Thayalan Rajeshkumar2, Mengyue Guo1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University 2005 Songhu Road, Jiangwan Campus Shanghai 200438 P. R. China lixinzh@fudan.edu.cn.
Abstract:
Guanidinate homometallic rare-earth ethyl complexes [LLn(μ2-η1:η2-Et)(Et)]2 (Ln = Y(1-Y), Lu(1-Lu)) and heterobimetallic rare-earth ethyl complexes LLn(Et)(μ2-η1:η2-Et)(μ2-η1-Et)(AlEt2) (Ln = Y(2-Y), Lu(2-Lu)) have been synthesized by the treatment of LLn(CH2C6H4NMe2-o)2 (L = (PhCH2)2NC(NC6H3iPr2-2,6)2) with different equivalents of AlEt3 in toluene at ambient temperature. Interestingly, the unprecedented rare-earth ethyne complex [LY(μ2-η1-Et)2(AlEt)]2(μ4-η1:η1:η2:η2-C2H2) (3-Y) containing a [C2H2]4- unit was afforded from 2-Y. The formation mechanism study on 3-Y was carried out by DFT calculations. Furthermore, the nature of the bonding of 3-Y was also revealed by NBO analysis. The reactions of LLn(CH2 C6H4NMe2-o)2 (Ln = Y, Lu) with AlEt3 (4 equiv.) in toluene at 50 °C produced firstly the non-Cp rare-earth ethylene complex LY(μ3-η1:η1:η2-C2H4)[(μ2-η1-Et)(AlEt2)(μ2-η1-Et)2(AlEt)] (4-Y), and the Y/Al ethyl complex LY[(μ2-η1-Et)2(AlEt2)]2 (5-Y) as an intermediate of 4-Y was isolated from the reaction of LY(CH2C6H4NMe2-o)2 with AlEt3 (4 equiv.) in toluene at -10 °C.
More Related Videos
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
07:28Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
Published on: November 27, 2015
Related Concept Videos
01:19Complexation Equilibria: The Chelate Effect
01:22EDTA: Chemistry and Properties
02:51Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
01:26EDTA: Auxiliary Complexing Reagents
02:52Stereoisomerism
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...