221041-10-7

Upstream product

• 366-18-7 [2,2]bipyridinyl 
• 186966-95-0 [Cu(CH3CN)2(κ(2)-P,P-1,1'-bis(diphenylphosphino)ferrocene)]BF4 

Relevant academic research and scientific papers

Novel copper(I) complexes containing 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a chelate and bridging ligand: Synthesis of tetrabridged dicopper(I) complexes [Cu2(μ-η1-C≡R)2(μ-dppf) 2] and X-ray crystal structure

Binuclear copper(I) complexes [Cu(κ2-P,P-dppf)(CH3CN)2][BF4] (1), [Cu(κ2-P,P-dppf)(bipy)]-[BF4] (2) containing the chelating dppf ligand (dppf = 1,1′-bis(diphenylphosphino)ferrocene) have been prepared by substitution reactions of the acetonitrile ligands from the complexes [Cu(CH3CN)4][BF4] and (1) with dppf and bipy, respectively. Similarly, the treatment of the complex [Cu2(μ-dppm)2(CH3CN)2][BF 4]2 with dppf in CH2Cl2 at room temperature gives the tetranuclear complex [Cu2(μ-dppm)2(κ2-P,P-dppf) 2][BF4]2 (3). The analogous bridging chloride tetranuclear complex [Cu2(μ-Cl)2(κ2-P,P-dppf)2] (4) has been also prepared by the addition of dppf to a solution in THF containing an equimolar mixture of CuCl and tetramethylethylenediamine. Complex 4 has been used as a precursor for μ-η1-alkynyl bridging dicopper(I) complexes containing the framework [Cu2(μ-dppf)2]. Complexes [Cu2(μ-η1-C≡CR)2(μ-dppf) 2] (R = C6H4CH3-4 (5), C6H5 (6), CH2OCH3 (7), CH2CH2CH3 (8), (η5-C5H4)Fe(η5-C 5H5) (9)) are obtained by the treatment of complex 4 with an excess of LiC≡CR hi THF. Complexes 5-9 can also be prepared from the reaction of an equimolar mixture of [Cu(C≡CR)]n and dppf in toluene at room temperature. The crystal structure of complex 5 has been determined by X-ray diffraction. The crystallographic asymmetric unit consists of three molecules of 5, all with related stereochemistries at their centers. The complex consists of two copper atoms linked by two bridging dppf ligands and two bridging alkynyl groups in a μ-η1 bonding arrangement with an almost planar [Cu2(μ-η1-C≡CR)2] framework. The arylethynyl groups are nearly linear (C≡C-C angles 174(2)-175(2)°), and the C≡C distances (1.20(2)-1.21(2) A?) are typical for cases of metal-acetylide σ-bonding. Both bridging dppf ligands are twisted from the eclipsed conformation (mean value 77(2)°) and also show a relatively large value of the angle (mean value 56.8(6)°) formed by the projection of the Cp?Cp axis of dppf onto the Cu?Cu axis. This seems to indicate that the molecular core [Cu2(μ-η1-C≡CC6H 4CH3-4)2] is a sterically demanding system that forces the dppf ligand to adopt a relatively strained conformation.

Heterobimetallic Cu-dppf (dppf = 1,1′-Bis(diphenylphosphino) ferrocene) complexes with click derived Ligands: A combined structural, electrochemical, spectroelectrochemical, and theoretical study

Heterodinuclear complexes of the form [(dppf)Cu(L)](BF4) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), where L are the chelating, substituted 4,4′-bis(1,2,3-triazole) or 4-pyridyl(1,2,3-triazole) ligands, were synthesized by reacting [Cu(dppf)(CH3CN)2](BF 4) with the corresponding click derived ligands. Structural characterization of representative complexes revealed a distorted-tetrahedral coordination geometry around the Cu(I) centers, with the donor atoms being the P donors of dppf and the N donors of the substituted triazole ligands. The local-pseudo symmetry around the iron center in all the investigated complexes of dppf is between that of the idealized D5h and D5d. Furthermore, for the complex with the mixed pyridine and triazole donors, the Cu-N bond distances were found to be shorter for the triazole N donors in comparison to those for the pyridine N donors. Electrochemical studies on the complexes revealed the presence of one oxidation and one reduction step for each. These studies were combined with UV-vis-near-IR and EPR spectroelectrochemical studies to deduce the locus of the oxidation process (Cu vs Fe) and to see the influence of changing the chelating click derived ligand on both the oxidation and reduction processes and their spectroscopic signatures. Structure-based DFT studies were performed to get insights into the experimental spectroscopic results. The results obtained here are compared with those of the complex [(dppf)Cu(bpy)](BF 4) (bpy = 2,2′-bipyridine). A comparison is made among bpy, pyridyl-triazole, and bis-triazole ligands, and the effect of systematically replacing these ligands on the electrochemical and spectroscopic properties of the corresponding heterodinuclear complexes is investigated.