Related Experiment Video
Updated: May 20, 2025
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
09:12
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
9.1K
Dynamic Copper(I) and Silver(I) Complexes of Tri-tert-butyl-cyclotriphosphane
Toni Grell1, Peter Wonneberger2, Divine Mbom Yufanyi2,3
1Dipartimento di Chimica, Università degli Studi di Milano, Via Camillo Golgi 19, Milan, Italy.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|March 26, 2025
Summary
This study details the synthesis of novel copper and silver complexes with cyclo-tris(tert-butyl)triphosphine. These complexes exhibit dynamic phosphorus-metal bonding in solution, a finding confirmed by NMR spectroscopy and computational analysis.
Area of Science:
- Coordination Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Cyclic phosphines are versatile ligands in coordination chemistry.
- Copper(I) and Silver(I) complexes are important in catalysis and materials science.
- Understanding ligand dynamics is crucial for designing new metal-based systems.
Purpose of the Study:
- To synthesize and characterize novel di- and tetranuclear copper(I) and silver(I) complexes.
- To investigate the solution behavior and bonding dynamics of these complexes.
- To elucidate the role of cyclo-(P3tBu3) as a bridging ligand.
Main Methods:
- Synthesis of metal complexes using cyclo-(P3tBu3) and Cu(I)/Ag(I) salts.
- X-ray diffraction for structural characterization of solid-state complexes.
- Low-temperature 31P{1H} NMR spectroscopy to study solution dynamics.
- Density Functional Theory (DFT) calculations to support experimental findings.
Main Results:
- Formation of di- and tetranuclear copper and silver complexes with bridging cyclo-(P3tBu3) ligands.
- Solid-state structures determined for complexes [Cu_n(micro-Br)_n{micro-cyclo-(P3tBu3)-kappaP1,kappaP2}_2] (n=2, 4) and [Ag_n(OTf)_n(CH3CN)_2n-2{micro-cyclo-(P3tBu3)-kappaP1,kappaP2}_2] (n=2, 4).
- Evidence for dynamic equilibrium involving reversible phosphorus-metal bond cleavage and formation in solution.
Conclusions:
- Cyclo-(P3tBu3) acts as a bridging ligand, forming polynuclear copper and silver complexes.
- These complexes display fluxional behavior in solution due to dynamic P-M bond exchange.
- DFT calculations confirm the observed dynamic equilibrium and provide insights into the reaction mechanism.
More Related Videos
09:45Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
10.3K
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
9.1K
Related Concept Videos
02:42Valence Bond Theory
8.4K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.4K
01:18Aromatic Hydrocarbon Cations: Structural Overview
2.6K
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group...
Removing one hydrogen from the intervening CH2 group...
2.6K
03:45Formation of Complex Ions
23.1K
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
23.1K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
41.0K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than...
41.0K
03:02Colors and Magnetism
11.4K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
11.4K
01:19Complexation Equilibria: The Chelate Effect
416
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
416