Cu(I) Complexes Comprising tetrahedral Mo2E2 or Mo2PE units (E = P, As, Sb) as Chelating Ligands

Chemistry. 2023 Dec 27:e202303455. doi: 10.1002/chem.202303455. Online ahead of print.ABSTRACTNovel isomorphous tetranuclear complexes, [(dppf)Cu( μ 3 , η 2:2:2 -E2{CpMo(CO)2}2]BF4 [E = P (1), As (4), Sb (5), (dppf = 1,1'-bis-(diphenylphosphino)-ferrocene)] and [(dppf)Cu( μ 3 , η 2:2:2 -PE{CpMo(CO)2}2]BF4 [E = As (2), Sb(3)] were synthesized from the reactions between [(dppf)Cu(MeCN)2][BF4] and tetrahedral molybdenum complexes containing unsubstituted homo- and hetero-diatomic group-15 elements [( μ , η 2:2 -E2{CpMo(CO)2}2] [E = P (A), As (D), Sb (E)] and [( μ , η 2:2 -PE{CpMo(CO)2}2] [E = As (B), Sb (C)], respectively. In all these products, the {Mo2E2} or {Mo2PE} moieties coordinate the Cu(I) center via a rare side-on η 2 -coordination mode. The X-ray structure analyses of [(dppf)Cu(μ3,η2:2:1-PSb{CpMo(CO)2}2][BF4] demonstrate, for the first time, the utilization of an η 1 -coordination mode for the ligand complex C to coordinate to the Cu(I) center. All the products were characterized by X-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. Electrochemical studies also revealed the formation of 1-5, and, further, to understand the structure and bonding of the products, theoretical calculations using density functional theory (DFT) were conducted.PMID:38149717 | DOI:10.1002/chem.202303455

Source: Chemistry - December 27, 2023 Category: Chemistry Authors: Bijan Mondal Manfred Scheer Source Type: research