Pincer-plus-one ligands in self-assembly with palladium(<scp>ii</scp>): a molecular square and a molecular tetrahedron

Behnia, Ava; Boyle, Paul D.; Fard, Mahmood Azizpoor; Blacquiere, Johanna M.; Puddephatt, Richard J.

doi:10.1039/c6dt04264c

Cited by 7 publications

(9 citation statements)

References 31 publications

(13 reference statements)

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“…This hexameric structure was a solid‐state phenomenon: the weak carbonyl‐Pd II bonds were readily broken upon dissolution of the crystals in polar solvents such as DMSO. Similar (tetrameric) assemblies have been reported by the groups of Hirao, Dell'Amico, and Blacquiere and Puddephatt and coworkers …”

Section: Introductionsupporting

confidence: 85%

Using Complementary Ligand Denticity to Direct Metallosupramolecular Structure about Metal Ions with Square‐Planar Geometry

Preston

Kruger

2020

ChemPlusChem

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An understanding of methods to control the structure of self‐assembled architectures is central to the efforts of chemists interested in self‐assembly synthesis. Metal ions with square‐planar geometry are a favorite of metallosupramolecular chemists, as there are only a limited number of possible ligand arrangements around the metal ion. Two such arrangements, firstly four monodentate donor sites (1,1,1,1), and secondly two monodentate donors and one bidentate donor (1,1,2) exemplify the symmetry interaction and ligand directed approaches, respectively. Symmetry interaction approaches using two bidentate sites (2,2) or a monodentate and tridentate site (1,3) have not received the same level of attention. In these arrangements, two complementary sites combine at the metal ion(s). This Minireview seeks to detail strategies employed to direct structure in systems with these arrangements, and is illustrated with key exemplars from the field.

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Section: Introductionsupporting

confidence: 85%

Using Complementary Ligand Denticity to Direct Metallosupramolecular Structure about Metal Ions with Square‐Planar Geometry

Preston

Kruger

2020

ChemPlusChem

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“…The complex [Pd(CH 2 CMe 2 C 6 H 4 )(κ 2 - N , N ′- L1 )], 1 , was prepared by ligand exchange from the corresponding 1,5-cyclooctadiene complex [Pd(CH 2 CMe 2 C 6 H 4 )(COD)] ,, and the known ligand N , N -bis(pyrid-2-ylmethyl)- N -(3-hydroxypropyl)amine, L1 (Scheme ). Complex 1 was thermally stable under dinitrogen atmosphere and was fully characterized by 1 H and 13 C NMR spectroscopy, including correlated 1 H– 1 H COSY, 1 H– 1 H NOESY, and 1 H– 13 C HSQC and HMBC NMR spectroscopy at both room temperature and −30 °C, as well as by mass spectrometry and IR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…The “cycloneophyl”, CH 2 CMe 2 C 6 H 4 , group ( A – D , Scheme ) has proven to be particularly valuable in studies of reactivity and selectivity in organopalladium chemistry. ,, The group is ideally suited to assess selectivity as it contains both Pd–Csp 3 and Pd–Csp 2 bonds, and the C(Me) 2 group prevents any complicating β-hydride elimination pathways. In order to further increase the reactivity of palladium(II) complexes toward oxidation by dioxygen or hydrogen peroxide, we have studied the cycloneophylpalladium(II) complex with the ligand HO(CH 2 ) 3 N(CH 2 –2-py) 2 , L1 , py = pyridyl .…”

Section: Introductionmentioning

confidence: 99%

Reactivity of a Palladacyclic Complex: A Monodentate Carbonate Complex and the Remarkable Selectivity and Mechanism of a Neophyl Rearrangement

et al. 2017

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The ligand N(CH2-2-C5H4N)2(CH2CH2CH2OH), L1, reacted with [Pd(CH2CMe2C6H4)(COD)] to give a new fluxional “cycloneophyl” organopalladium complex [Pd(CH2CMe2C6H4)(κ2-L1)], 1, which on attempted recrystallization from THF gave the monodentate carbonate complex [Pd(CO3)(κ3-L1)], 2. Complex 2 was prepared in designed syntheses by reaction of [PdCl(κ3-L1)]+ with silver carbonate or by reaction of [Pd(OH)(κ3-L1)]+ with CO2. Complex 1 reacted with aqueous CO2 to give the cationic neophylpalladium complex [Pd(CH2CMe2C6H5)(κ3-L1)]+(HCO3)−, 6. Complex 6 reacts with hydrogen peroxide to give complex 2 with release of a mixture of organic products, the major one being 2-phenyl-2-butanol, PB. The formation of PB involves a neophyl rearrangement with the unprecedented preference for methyl over phenyl migration. A mechanistic basis for this unexpected reaction is proposed, involving β-carbon elimination at a palladium(IV) center.

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“…Similar (tetrameric) assemblies have been reported by the groups of Hirao, [30] Dell'Amico, [31] and Blacquiere and Puddephatt and coworkers. [32] However, this Minireview is primarily concerned with solution-persistent structures, which in 1,3 systems require stronger monodentate donors. For example, Nabeshima and coworkers synthesised a ligand with a terpyridine site, a biphenyl linker, and a monodentate pyridyl site (L15).…”

Section: 3 Assembliesmentioning

confidence: 99%

Cover Feature: (ChemPlusChem 5/2020)

Preston

Kruger

2020

ChemPlusChem

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The Cover Feature shows a jigsaw with some of the structures discussed in this Minireview. This overview details two of the less‐explored arrangements of ligands around square‐planar metal ions, and how they can be used to assemble exciting metallosupramolecular architectures. The Lego bricks symbolize the construction of complex structures from simple componentry. More information can be found in the Minireview by D. Preston and P. Kruger (DOI: 10.1002/cplu.202000019). The authors thank the Lego Group for allowing them to include the bricks in this image.

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Pincer-plus-one ligands in self-assembly with palladium(ii): a molecular square and a molecular tetrahedron

Cited by 7 publications

References 31 publications

Using Complementary Ligand Denticity to Direct Metallosupramolecular Structure about Metal Ions with Square‐Planar Geometry

Using Complementary Ligand Denticity to Direct Metallosupramolecular Structure about Metal Ions with Square‐Planar Geometry

Reactivity of a Palladacyclic Complex: A Monodentate Carbonate Complex and the Remarkable Selectivity and Mechanism of a Neophyl Rearrangement

Cover Feature: (ChemPlusChem 5/2020)

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