LCu(μ-X)2CuL compounds: An induced cuprophilic interaction

Abstract

A trio of dimeric copper(I) complexes of the formula [(Ph 3 P)Cu(μ-X) 2 Cu(PPh 3)] (X = OC 6 F 5 , 1, OC 4 F 9 , 2, OCPh(CF 3) 2 , 3) were prepared and characterized by X-ray crystallography, elemental analysis, and NMR spectroscopy (1 H, 13 C, 19 F, 31 P), as was the monomeric [(cy 3 P)Cu(OC 4 F 9)] (cy = cyclohexyl,4). Solution conductivity studies demonstrate that all three new dinuclearcompounds, as well as the known [(Ph 3 P)Cu(μ-OC 4 H 9) 2 Cu(PPh 3)], 2-H, are neutral species in solution and do not rearrange into ion pairs. The fold angle () varies among these four dimers and the Cu(I) … Cu(I) distance in the structure of 2, 2.8315(5) Å, is cuprophilic. The Cu(I) … Cu(I) distances for 1, 2-H, and 3 are 3.0533(5), 2.890(2), and 3.0169(6) Å respectively.Density functional theory (DFT) calculations were performed on 1, 2, 3, and 2-H, as well as the hypothetical 1-H, and several related models. FivePMe 3 models, 1(Me), 1-H(Me), 2(Me), 2-H(Me), and 3(Me) were also studied as well as five monomers [(Me 3 P)CuX]1-mon, 1-H(mon), 2-mon, 2-H(mon), and 3-mon to understand the electronic reasons for folding in this group of compounds. A Natural Energy Decomposition Analysis (NEDA) indicates that electrostatic stabilizations are the dominant factor governing the strength of interaction between monomeric fragments in 1(Me)-3(Me). NBO analysis reveals that 1(Me) and 1-H(Me) do not display any cuprophilic interactions. The folding angle observed in 2(Me), 2-H(Me), and 3(Me), which is correlated with an increased delocalization from the oxygen 2p z lone pairs, brings the metal centers into sufficient propinquity to have weak Cu … Cu orbital interactions. Weak luminescence behavior at room-temperature is also consistent with these assignments.

On the Way to a Trisanionic {Cu3O2} Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands

“…Monodeprotonated species KHpin F was synthesized by addition of KH to equimolar perfluoropinacol (H 2 pin F ). The heteroleptic Cu I complexes were synthesized by a modified alcoholysis route (Scheme ). The anionic Cu I complexes K[(Ph 3 P)Cu(pin F )] ( 4 ) and K[(Cy 3 P)Cu(pin F )] ( 5 ) were synthesized by the reaction of {Cu(mes)} n (mes=mesityl) with KHpin F , immediately followed by the addition of the PR 3 L‐donor ligand.…”

“…Therefore, K⋅⋅⋅O and K⋅⋅⋅F interactions facilitate assembly of the {Cu 3 (μ 3 ‐O) 2 } cores and reduction of O 2 . Several heteroleptic Cu I –phosphine complexes with bridging fluorinated alkoxide compounds have also been reported …”

“…[24] Severalh eteroleptic Cu I -phosphine complexesw ith bridging fluorinated alkoxide compounds have also been reported. [25] More recently complexes with ab identate perfluoropinacolate [(pin F ) 2À ]l igand were prepared for reactivity studies of [M II (pin F ) 2 ] 2À (M = Fe II , [23,26] Co II , [23,26] Ni II , [26] Cu II , [26] and Zn II ). [23,26] Herein, we reportt he synthesis and characterization of as eries of anionic Cu I complexes of the form A[(R 3 P)Cu(pin F )] (A = cation).…”

Synthesis, Structural Characterization, and CO2Reactivity of a Constitutionally Analogous Series of Tricopper Mono-, Di-, and Trihydrides

“…Addition of electron-deficient perfluoro phenol (pK a [MeCN] = 20.1) 86 did result in exhaustive protonolysis, yielding a new species with 1 H and 19 F NMR characteristics consistent with the tricopper bis(pentafluorophenolate) cation, [LCu 3 (OC 6 F 5 ) 2 ][BArF] (Scheme 2). 88 The thermodynamics of hydride protonolysis and phenolate binding cannot be strictly disentangled; however, this suggests a hydricity for the dihydride cation, 3, below ca. 48.5 kcal/mol.…”

Luminescence of Lanthanide Complexes with Perfluorinated Alkoxide Ligands

“…Our group has previously used fluorinated alkoxides and aryloxides to produce a family of complexes including an unusual trivalent Cu species, three-coordinate transition-metal complexes in exclusively O-donor environments, and rare high-spin square-planar metal centers. , To date, five 3d metals (Fe, − Co, , Ni, Cu, ,,,− and Zn , ) have been prepared as homonuclear, homoleptic [M­(pin F ) 2 ] 2– and [M­(OC 4 F 9 ) n ] m − complexes, heteroleptic [(R 3 P) 2 M­(OR F ) 2 ] complexes, and main-group species Tl­(OC 4 F 9 ) . Thus, with the goal of preparing luminescent Ln III complexes with fluorinated alkoxide ligands and homoleptic O-donor environments, we undertook the synthesis and characterization of a series of Ln III complexes, whose syntheses are shown in Scheme , with [OC 4 F 9 ] − ligands, and in Scheme for [pin F ] 2– (perfluoropinacolate) ligands.…”