Multinuclear Cu(I) Clusters Featuring a New Triply Bridging Coordination Mode of Phosphaamidinate Ligands

Rathnayaka, Suresh C.; Lindeman, Sergey V.; Mankad, Neal P.

doi:10.1021/acs.inorgchem.8b01422

Cited by 9 publications

(12 citation statements)

References 39 publications

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“…Surprisingly, the phosphaamidinates did not behave as their formamidinate counterparts; instead, we previously reported their assembly into a hexa- and tetracopper(I) clusters, respectively (Table ). In these multinuclear clusters, the negatively charged phosphide units were found to bridge three Cu(I) ions. Apparently, the negative charge should be valence-trapped on nitrogen to facilitate μ 2 -coordination of the 3-atom bridge; delocalization of negative charge on phosphorus instead favors binding to three copper centers.…”

Section: Resultsmentioning

confidence: 99%

“…Phosphaamidinates ( n )–( p ) were rationally designed to incorporate both neutral and anionic donors. The anionic charge delocalization onto phosphorus results in μ 3 -bridging coordination, but valence-trapping the charge on nitrogen allows the isolation of a dicopper complex. An ideal ligand system that would stabilize all three redox states of a Cu 4 (μ 4 -S) complex is yet to be discovered.…”

Section: Discussionmentioning

confidence: 99%

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Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu₄(μ₄-S) Model Compounds of the Cu_Z Active Site of Nitrous Oxide Reductase (N₂OR)

et al. 2020

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Model compounds have been widely utilized in understanding the structure and function of the unusual Cu4(μ4-S) active site (CuZ) of nitrous oxide reductase (N2OR). However, only a limited number of model compounds that mimic both structural and functional features of CuZ are available, limiting insights about CuZ that can be gained from model studies. Our aim has been to construct Cu4(μ4-S) clusters with tailored redox activity and chemical reactivity via modulating the ligand environment. Our synthetic approach uses dicopper(I) precursor complexes (Cu2L2) that assemble into a Cu4(μ4-S)L4 cluster with the addition of an appropriate sulfur source. Here, we summarize the features of the ligands L that stabilize precursor and Cu4(μ4-S) clusters, along with the alternative products that form with inappropriate ligands. The precursors are more likely to rearrange to Cu4(μ4-S) clusters when the Cu(I) ions are supported by bidentate ligands with 3-atom bridges, but steric and electronic features of the ligand also play crucial roles. Neutral phosphine donors have been found to stabilize Cu4(μ4-S) clusters in the 4Cu(I) oxidation state, while neutral nitrogen donors could not stabilize Cu4(μ4-S) clusters. Anionic formamidinate ligands have been found to stabilize Cu4(μ4-S) clusters in the 2Cu(I):2Cu(II) and 3Cu(I):1Cu(II) states, with both the formation of the dicopper(I) precursors and subsequent assembly of clusters being governed by the steric factor at the ortho positions of the N-aryl substituents. Phosphaamidinates, which combine a neutral phosphine donor and an anionic nitrogen donor in the same ligand, form multinuclear Cu(I) clusters unless the negative charge is valence-trapped on nitrogen, in which case the resulting dicopper precursor is unable to rearrange to a multinuclear cluster. Taken together, the results presented in this study provide design criteria for successful assembly of synthetic model clusters for the CuZ active site of N2OR, which should enable future insights into the chemical behavior of CuZ.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu₄(μ₄-S) Model Compounds of the Cu_Z Active Site of Nitrous Oxide Reductase (N₂OR)

et al. 2020

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“…In previous studies by our group and others, we have found this method produces results within a reasonable amount of error for gold and copper nanoparticle systems. 7 Initial geometries for Cu 22 to phenyl groups to obtain Cu 4 (PN-(C 6 H 5 ) 2 CH) 4 (2a). Additionally, the R-groups in the ligands of 1a and 2a were further reduced to methyl/hydrogen groups to obtain Cu 4 (SN 2 C 3 H 7 ) 4 (1b), Cu 4 (SN 2 CH 3 ) 4 (1c), Cu 4 (PN-(CH 3 ) 2 CH) 4 (2b), and Cu 4 (PNH 2 CH) 4 (2c).…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…Initial geometries for Cu 4 (SN 2 C 7 H 11 ) 4 ( 1a ), Cu 4 (PN(C 9 H 11 ) 2 CH) 4 , and Cu 6 (SC 7 H 4 NO) 6 – were obtained from previous experimental reports. Prior to geometry optimization, we reduced the mesitylene group in the ligand of Cu 4 (PN(C 9 H 11 ) 2 CH) 4 to phenyl groups to obtain Cu 4 (PN(C 6 H 5 ) 2 CH) 4 ( 2a ). Additionally, the R-groups in the ligands of 1a and 2a were further reduced to methyl/hydrogen groups to obtain Cu 4 (SN 2 C 3 H 7 ) 4 ( 1b ), Cu 4 (SN 2 CH 3 ) 4 ( 1c ), Cu 4 (PN(CH 3 ) 2 CH) 4 ( 2b ), and Cu 4 (PNH 2 CH) 4 ( 2c ).…”

Section: Methodsmentioning

confidence: 99%

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Computational Comparative Analysis of Small Atomically Precise Copper Clusters

2020

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Atomically precise copper clusters (APC) have attracted attention for their promise in sensing, water remediation, and electrochemical technologies. However, smaller-sized APCs and the evolution of their properties as a function of size and composition are not clearly understood. Here, we have performed an investigation into the electronic structure, geometry, and optical properties of small atomically precise copper clusters using density functional theory (DFT) and time-dependent DFT. Through comparative analysis, we show that the electronic structures of the experimentally characterized clusters, Cu4(PN(C6H5)2CH)4 and Cu4(SN2C7H11)4, are similar with the closed-shell superatom character 1S21P2. By changing the ligand on Cu4(PN(C6H5)2CH)4 and Cu4(SN2C7H11)4, there were no major changes observed in the tetrahedral Cu4 core geometry, electronic structure, or optical spectra. However, a change in the anchor atom causes an increase in the electronic gap and induces a hypochromic shift in the onset peak in the optical spectrum of the small clusters. Increasing the copper core size showed small changes Cu–Cu bond lengths, lower electronic gap values, and a bathochromic shift in the optical spectra. Computational results not only provide detailed physical insight into APCs but also aid in identifying compound compositions of small atomically precise nanoclusters from data collected in the experiment.

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Luminescent Tetranuclear Copper(I) and Gold(I) Heterobimetallic Complexes: A Phosphine Acetylide Amidinate Orthogonal Ligand Framework for Selective Complexation

Shubham,

Naina,

Roesky

2024

Chemistry A European J

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The synthesis of phosphine acetylide amidinate stabilized copper(I) and gold(I) heterobimetallic complexes was achieved by reacting ligand [{Ph2PC≡CC(NDipp)2}Li(thf)3] (Dipp = N,N’‐diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph2PC≡CC(NDipp)2}2Cu2] and the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2]. {Ph2PC≡CC(NDipp)2}2Cu2] features a Cu2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic CuI/AuI complexes [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X = Cl, C6F5). In these reactions the central ring structure is retained. In contrast, when the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2] was reacted with CuX (X = Cl, Br, I and Mes), the reaction led to rearrangement of the central ring structure to give [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X = Cl, Br, I and Mes), which feature the same the eight membered Cu2 ring as above. These compounds were also synthesized by a one‐pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties.

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Multinuclear Cu(I) Clusters Featuring a New Triply Bridging Coordination Mode of Phosphaamidinate Ligands

Cited by 9 publications

References 39 publications

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu₄(μ₄-S) Model Compounds of the Cu_Z Active Site of Nitrous Oxide Reductase (N₂OR)

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu₄(μ₄-S) Model Compounds of the Cu_Z Active Site of Nitrous Oxide Reductase (N₂OR)

Computational Comparative Analysis of Small Atomically Precise Copper Clusters

Luminescent Tetranuclear Copper(I) and Gold(I) Heterobimetallic Complexes: A Phosphine Acetylide Amidinate Orthogonal Ligand Framework for Selective Complexation

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Multinuclear Cu(I) Clusters Featuring a New Triply Bridging Coordination Mode of Phosphaamidinate Ligands

Cited by 9 publications

References 39 publications

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu4(μ4-S) Model Compounds of the CuZ Active Site of Nitrous Oxide Reductase (N2OR)

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu4(μ4-S) Model Compounds of the CuZ Active Site of Nitrous Oxide Reductase (N2OR)

Computational Comparative Analysis of Small Atomically Precise Copper Clusters

Luminescent Tetranuclear Copper(I) and Gold(I) Heterobimetallic Complexes: A Phosphine Acetylide Amidinate Orthogonal Ligand Framework for Selective Complexation

Contact Info

Product

Resources

About

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu₄(μ₄-S) Model Compounds of the Cu_Z Active Site of Nitrous Oxide Reductase (N₂OR)

Impact of Electronic and Steric Changes of Ligands on the Assembly, Stability, and Redox Activity of Cu₄(μ₄-S) Model Compounds of the Cu_Z Active Site of Nitrous Oxide Reductase (N₂OR)