Syntheses and coordination studies of 2-(diphenylphosphinomethyl)pyridine and its oxide towards mercury(II)

Padron, Daniel A.; Klausmeyer, Kevin K.

doi:10.1016/j.poly.2012.01.001

Cited by 12 publications

(2 citation statements)

References 35 publications

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“…The versatile coordinating behavior of hemilabile P–N-compounds is a widely used property not only in coordination chemistry but also in the fields of catalysis, bioinorganic chemistry, or material science. − A comprehensive design of such multidentate phosphine ligands is beneficial when trying to provoke or improve specific properties of the resulting metal complex, e.g., luminescence or catalytic activity. A broad variety of phosphine and phosphine oxide ligands with nitrogen containing aromatic substituents directly bonded to phosphorus have been published. − Despite the fact that these compounds do not allow for any flexibility of the ligand, they show impressive material properties, such as luminescence or catalytic activity in addition to a rich coordination chemistry. − For the application in transition-metal catalysis, a certain conformational flexibility of the ligand can be beneficial, as possible transition states can be stabilized more easily. − The benefit of flexibility in catalysis has been demonstrated for enzymatic systems and has recently been discussed for a variety of other catalyst classes by Sigman et al − The steric demand of the phosphine ligand when coordinating to a metal can be varied by changing the substituents on phosphorus accordingly.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

et al. 2021

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The syntheses of a sterically demanding, multidentate bis(quinaldinyl)phenylphosphine oxide ligand and some Cu(I) and Ag(I) complexes thereof are described. By introducing a methylene group between the quinoline unit and phosphorus, the phosphine oxide ligand gains additional flexibility. This specific ligand design induces not only a versatile coordination chemistry but also a rarely observed and investigated behavior in solution. The flexibility of the birdlike ligand offers the unexpected opportunity of open-wing and closed-wing coordination to the metal. In fact, the determined crystal structures of these complexes show both orientations. Investigations of the ligand in solution show a strong dependency of the chemical shift of the CH 2 protons on the solvent used. Variable-temperature, multinuclear NMR spectroscopy was carried out, and an interesting dynamic behavior of the complexes is observed. Due to the introduced flexibility, the quinaldinyl substituents change their arrangements from open-wing to closed-wing upon cooling, while still staying coordinated to the metal. This change in conformation is completely reversible when warming up the sample. Based on 2D NMR spectra measured at −80 °C, an assignment of the signals corresponding to the different arrangements was possible. Additionally, the copper(I) complex shows reversible redox activity in solution. The combination of structural flexibility of a multidentate ligand and the positive redox properties of the resulting complexes comprises key factors for a possible application of such compounds in transition-metal catalysis. Via a reorganization of the ligand, occurring transition states could be stabilized, and selectivity might be enhanced.

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Section: Introductionmentioning

confidence: 99%

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

et al. 2021

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“…11, right). [ [48][49][50][51][52]. This unit is also present in polymeric complexes containing bis-bidentate bridging ligands [53].…”

Section: Interaction Da (å) Ha (å) D-ha ( O ) Symmetry Operamentioning

confidence: 99%

Doubly Thiocyanato(S,N)-Bridged Dinuclear Complexes of Mercury(II) from the Use of 2-pyridyl Oximes as Capping Ligands

Danelli¹,

Lada²,

Raptopoulou³

et al. 2015

CIC

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The reactions between Hg(SCN) 2 and the 2-pyridyl oximes, 2-pyridine aldoxime (paoH), methyl 2-pyridyl ketone oxime (mepaoH), pyridine-2-amidoxime (NH 2 paoH) and di-2-pyridyl ketone oxime (dpkoxH), have been investigated. The products in Me 2 CO or Me 2 CO/MeOH are the dinuclear complexes [Hg 2 (SCN) 4 (paoH) 2 ] (1), [Hg 2 (SCN) 4 (mepaoH) 2 ] (2), [Hg 2 (SCN) 4 (NH 2 paoH) 2 ] (3) and [Hg 2 (SCN) 4 (dpkoxH) 2 ] (4), whose structures have been determined by single-crystal X-ray crystallography. The molecular structures consist of centrosymmetric dinuclear molecules in which the two Hg II ions are bridged by two bidentate bridging 1 : 1 :: (: 1,3) SCNgroups forming a planar (1, 2) or non-planar (3, 4), 8-membered metallacyclic ring. The Hg II centers are each chelated by a N(2-pyridyl), N(oxime)-bidentate ligand and are bound to one terminal S-bonded thiocyanato group. Due to the very long Hg II-N (bridging SCN-) distances in 3, this complex can also be described as pseudodimer. The second 2-pyridyl ring of each dpkoxH ligand in 4 remains uncoordinated. The 2D lattice of 1 and 2 is built through H-bonding and-stacking interactions. Hydrogen bonds and S...S interactions generate 3D networks in 3 and 4. The IR spectra of the complexes are discussed in terms of the coordination modes of the ligands involved (SCN-, 2-pyridyl oximes). 1 H NMR spectra in d 6-DMSO indicate that the complexes decompose in solution.

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Syntheses and Coordination Studies of 2‐(Phosphanylmethyl)pyridine Dioxide toward Silver (I)

Padron

Klausmeyer

2012

Eur J Inorg Chem

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The coordination properties of the 2‐[(diphenylphosphanyl)methyl]pyridine N,P‐dioxide ligand towards three different silver(I) salts are described. The molecular structures of the coordination complexes obtained showed a strong dependence on the 2‐[(diphenylphosphanyl)methyl]pyridine N,P‐dioxide ligand and the binding ability of the counterion. The strongly binding trifluoroacetate ion yielded a unique planar silver cluster complex, whereas the less strongly binding triflate and BF4– complexes yielded polymeric structures. The synthesized complexes were fully characterized by elemental analysis and multinuclear NMR spectroscopy techniques. The crystal structures were determined by single‐crystal X‐ray crystallography.

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Syntheses and coordination studies of 2-(diphenylphosphinomethyl)pyridine and its oxide towards mercury(II)

Cited by 12 publications

References 35 publications

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

Doubly Thiocyanato(S,N)-Bridged Dinuclear Complexes of Mercury(II) from the Use of 2-pyridyl Oximes as Capping Ligands

Syntheses and Coordination Studies of 2‐(Phosphanylmethyl)pyridine Dioxide toward Silver (I)

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