Di ZhuChina university of petroleum-beijing · applied chemistry
Di Zhu
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Publications (15)
Oxidation of ((Me)BDI)Rh(cyclooctene) ((Me)BDI = [2,6-Me2C6H3NCMe]2CH) with Br2 or I2 produces paramagnetic halide-bridged Rh(II) dimers [((Me)BDI)Rh]2(μ-X)2 without a direct Rh-Rh bond. Steric factors are proposed to play a key role in preventing the formation of Rh-Rh bonded alternative structures.
This perspective summarizes the chemistry of platinum metal complexes of β-diiminate ligands bearing aryl groups at the nitrogen atoms. While β-diiminate ligands mostly coordinate in a κ(2)-N,N' mode, palladium complexes have a tendency to rearrange to C-bound structures (κ(2)-N,C or μ-N,N':C). Diiminate ligands are remarkably effective at stabiliz...
Die Kupplung von HSiEt3 und verwandten Silanen an β‐Diiminat‐Liganden erfordert eine Reihe von Si‐H‐, C‐H‐ und Si‐C‐Bindungsbrüchen und ‐bildungen. Der Komplex 1 verliert eine Et(Si)‐Gruppe als Ethan und kuppelt das verbleibende SiEt2H‐Fragment an eine benzylische Methylgruppe des Ligandgerüsts. DFT‐Rechnungen zufolge verläuft die Reaktion über Sil...
The coupling of HSiEt(3) and related silanes to β-diiminate ligands is achieved through a series of SiH, CH, and SiC bond breaking and bond forming reactions. Complex 1 loses an Et(Si) group as ethane and couples the remaining SiEt(2) H fragment to a benzylic methyl group of the ligand skeleton. According to DFT calculations, the reaction involv...
The formally Co(0) complex LCo(N2) (L = 2,6-bis(2,6-dimethylphenyliminoethyl)pyridine) can be prepared via either Na/Hg reduction of LCoCl2 or hydrogenolysis of LCoCH2SiMe3. In the latter reaction, LCoH could be trapped by reaction with N≡CC6H4-4-Cl to give LCoN═CHC6H4-4-Cl. LCo(N2) reacts with many alkyl and aryl halides RX, including aryl chlorid...
Knowledge about bonding in diiminepyridine (L) halide, alkyl, and dinitrogen complexes of the metals iron, cobalt, and nickel is summarized, and two new examples are added to the set: L(1)Ni(Me) and L(1)Ni(N(2)). Reactivity of these types of complexes is discussed in terms of organic radical chemistry. New C-C couplings with L(2)CoAr complexes are...
Reaction of LCoCH2SiMe3 (L = 2,6-bis[2,6-dimethylphenyliminoethyl]pyridine) with H2 produces LCo(N2), presumably via intermediate LCoH. Reaction of LCo(N2) (prepared in this way or via reaction of LCoCl2 with Na/Hg) with aryl halides ArX (X = Cl, Br, I) produces LCoAr and LCoX in a ratio depending on the nature of Ar and X. For X = Cl, the reaction...
(Py)2CoR2 (R = CH2SiMe3) is easily prepared from (Py)4CoCl2 and RLi. It is fairly stable at room temperature and serves as a convenient source of CoR2 for transfer to other ligands. Unfortunately, (Py)2CoR2 was obtained only as an oil, but the structure of the related complex (Py)2CoR′2 (R′ = CH2CMe2Ph) could be confirmed by a single-crystal X-ray...
Relative metal−ligand binding strengths for the ZnCl2 and low-spin CoIMe fragments and a variety of diiminepyridine (DIP)-like ligands have been calculated at the DFT level. The assumption of a linear energy relation ΔEstab(F,L) = αFσL + βFπL for the relative binding energy of fragment F to ligand L was used to derive scales for ligand parameters σ...
A highly efficient copper-catalyzed system using phosphoramidite as ligands was applied to N-arylation of alkylamines and N(H)-heterocycles with aryl iodides and heteroaryl bromides. The reactions were carried out in relative mild conditions and good to excellent yields were obtained.
A highly efficient copper-catalyzed system using commercially available racemic 1,1′-binaphthyl-2,2′-diol (rac-BINOL) as the ligand was developed for amination of aryl halides and heteroaryl halides with alkyl amines and NH heterocycles. Good to high yields were obtained for aryl bromides and heteroaryl chlorides. The commercially available rac-BIN...
A mild and efficient copper-catalyzed system for the coupling of aryl iodides and thiols was developed using a readily prepared and highly stable oxime–phosphine oxide ligand. Good to excellent yields were obtained. Aryl sulfides are valuable intermediates in organic syn-thesis and are of great importance to the pharmaceutical industry. 1 Transitio...
A mild and highly efficient copper-catalyzed system for N-arylation of alkylamines with aryl iodides using binaphthol-based phosphoramidites as ligands was developed. The phosphoramidite ligands are stable, cost-effective and easily prepared from inexpensive, commercially available starting materials using a simple, efficient method.
A highly effective method for palladium-catalyzed Suzuki–Miyaura coupling of aryl bromides and arylboronic acids using novel 2-(diphenylphosphino) benzaldoxime ligand was developed. The new catalytic system based on Pd(OAc) 2 and the readily prepared and air stable ligand afforded high turnover numbers (up to 10 4) for a variety of substrates.
A mild and efficient copper-catalyzed system for N-arylation of alkylamines and N–H heterocycles with aryl iodides using a novel, readily prepared and highly stable oxime-functionalized phosphine oxide ligand was developed. The coupling reactions could even be performed in solvent-free conditions with moderate to good yields.