Tetraimido Sulfuric Acid H2S(NtBu)4—Valence Isoelectronic to H2SO4

Jung, Jochen; Münch, Annika; Herbst‐Irmer, Regine

doi:10.1002/anie.202014426

Cited by 13 publications

(10 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The tetraimido sulfate ligand family also represents a platform to investigate d‐metal exchange coupling, which was applied for Co II and Mn II [15] . Sulfur offers great flexibility in the complex geometry while the harder nitrogen atoms ensure an optimal coordination mode around the metal center, resulting in a great synergy [25,27–29] . Lanthanide complexes are easily accessible through metathesis reactions and for that purpose, lithium precursors are convenient to use.…”

Section: Introductionmentioning

confidence: 99%

“… [15] Sulfur offers great flexibility in the complex geometry while the harder nitrogen atoms ensure an optimal coordination mode around the metal center, resulting in a great synergy. [ 25 , 27 , 28 , 29 ] Lanthanide complexes are easily accessible through metathesis reactions and for that purpose, lithium precursors are convenient to use. However, our recent work showed that the successful optimization of the magnetic properties is limited by LiHal co‐complexation.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets

Lüert

Legendre

Herbst‐Irmer

2022

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Based on the potassium [{S(tBuN)2(tBuNH)}2K3(tmeda)‐K3{(HNtBu)(NtBu)2S}2] (1) and sodium precursors [S(tBuN)3(thf)3‐Na3SNa3(thf)3(NtBu)3S] (2), [S(tBuN)3(thf)3Na3{(HNtBu)(NtBu)2S}] (3) and [(tmeda)3S‐{Na3(NtBu)3S}2] (4) the syntheses and magnetic properties of three mixed metal triimidosulfite based alkali‐lanthanide‐metal‐cages [(tBuNH)Dy{K(0.5tmeda)}2{(NtBu)3S}2]n (5) and [ClLn{Na(thf)}2{(NtBu)3S}2] with Ln=Dy (6), Er (7) are reported. The corresponding potassium (1) and sodium (2–4) based cages are characterized through XRD and NMR experiments. Preventing lithium chloride co‐complexation led to a significant increase of SMM performance to previously reported sulfur‐nitrogen ligands. The subsequent DyIII‐complexes 5 and 6 display slow relaxation of magnetization at zero field, with relaxation barriers U=77.0 cm−1 for 5, 512.9 and 316.3 cm−1 for 6, respectively. Significantly, the latter complex 6 also exhibits a butterfly‐shaped hysteresis up to 7 K.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets

Lüert

Legendre

Herbst‐Irmer

2022

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…The existence of the dianionic species [P{N(H)Ph}(NPh respectively. [24] Alongside, few research groups have contributed to the transition metal complexes of these polyimido anions. Collins et al have obtained various mononuclear Ni(II) complexes of the mono-anionic [Ph 2 P(NSiMe 3 ) 2 ] À having PN 2 Ni ring(s), 29 (Figure 5a).…”

Section: Dehnicke Et Al Have Studied Neutral Mono Functionalizedmentioning

confidence: 99%

“…All of these complexes provide two separate chelating N−P−N sites at opposite ligand faces, comprising either one of a) the di(amino) arrangement of the type P(NH) 2 , b) the di(imino) arrangement of the type PN 2 , or c) the mixed amino imino arrangement of the type P(N)(NH). Recently, Stalke and co‐workers have isolated the sulfur analogue of the species 25 and 22 , the tetra(imido)sulphate dianion [S(NR) 4 ] 2− and the neutral amido‐imido sulfuric acid [S(NHR) 2 (NR) 2 ], respectively [24] …”

Section: Introductionmentioning

confidence: 99%

Polyanionic Imido‐P(V) Ligands: From Transition Metal Complexes to Coordination Driven Self‐Assemblies

Sarkar

Rajasekar

Jose

et al. 2021

The Chemical Record

View full text Add to dashboard Cite

The chemistry of the imido‐anions of the main group elements has been studied for more than three decades. The imido (NR)− group is isoelectronic to the oxo (=O) group and can coordinate with metal ions through its lone pairs of electrons. The polyimido‐P(V) anions are well explored as they resemble the phosphorus oxo moieties such as H3PO4, H2PO4−, HPO42− and PO43− species. These imido anions are typically generated using strong main group organometallic reagents such as nBuLi, Et2Zn, Me3Al and nBu2Mg, etc. As a result, their coordination chemistry has been restricted to reactions in anhydrous aprotic solvents for a few main group metal ions. This account presents our findings on using certain soft transition metal such Ag(I) and Pd (II) for isolating these imido‐P(V) anions as their corresponding self‐assembled clusters and cages. Using the various salts of Ag(I) ions in reaction with 2‐pyridyl (2Py) functionalized phosphonium salts and phosphoric triamides, we obtained the mono‐ and dianionic form of these imido ligands {[P(N2Py)2(NH2Py)2]−, [P(N2Py)2(NH2Py)]−, [PO(N2Py)(NH2Py)2]2−} and derived interesting examples of tri, penta, hepta and octanuclear Ag(I) clusters. Interestingly, by using the salts of Pd (II) ions, the elusive imido‐phosphate trianions of the type [(RN)3PO]3− (R=tBu, cHex, iPr) were generated in a facile one pot reaction as their corresponding tri‐ and hexanuclear clusters of the type {Pd3[(NR)3PO](OAc)3}n (n=1 or 2). These trianions acts as a cis‐coordinated hexadentate ligand for a trinuclear Pd (II) cluster and serve as the polyhedral building units for constructing hitherto unknown family of neutral cages in tetrahedral {Pd3[(NiPr)3PO]4(L)6} and cubic {Pd3[(NiPr)3PO]8(L)12} structures in the presence of suitable linker ligands (L2−). These cages show interesting host‐guest chemistry and post‐assembly reactions. Remarkably, by employing chiral tris(imido)phosphate trianions, enantiopure chiral cages of the type [(Pd3X*)4(L)6], ([X*]3−=RRR‐ or SSS‐[PO(N(*CH(CH3)Ph)3]3−), were synthesized and used for the chiral‐recognition and enantio‐separation of small racemic guest molecules. Some of these chiral cages were also shown to exhibit polyradical framework structures. In future, these and other similar types of cages are envisioned as potential molecular vessels for performing the reactions in their confined environment. The enantiomeric cages can be probed for asymmetric catalysis and the separation of a range of small chiral molecules.

show abstract

“… [17] We have been already successful employing those ligands to d‐block SMMs with the [MeS(N t Bu)] − ligand in [Co{(N t Bu) 3 SMe} 2 ], (with U eff =75 cm −1 , T B =2.6 K and a hysteresis loop at 2 K), [18] accompanying of a series of complexes with the [S(N t Bu) 4 ] 2− anion. [ 19 , 20 ] This fuelled the idea to transfer the ligand concept to f‐block metals. First results are presented in here.…”

Section: Introductionmentioning

confidence: 99%

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes

Jung

Benner

Herbst‐Irmer

et al. 2021

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Lanthanide ions are particularly well-suited for the design of single-molecule magnets owing to their large unquenched orbital angular momentum and strong spin-orbit coupling that gives rise to high magnetic anisotropy. Such nanoscopic bar magnets can potentially revolutionize highdensity information storage and processing technologies, if blocking temperatures can be increased substantially. Exploring non-classical ligand scaffolds with the aim to boost the barriers to spin-relaxation are prerequisite. Here, the syn-thesis, crystallographic and magnetic characterization of a series of each isomorphous mono-and dinuclear lanthanide (Ln = Gd, Tb, Dy, Ho, Er) complexes comprising tetraimido sulfate ligands are presented. The dinuclear Dy complex [{(thf) 2 Li(NtBu) 2 S(tBuN) 2 DyCl 2 } 2 • ClLi(thf) 2 ] (1c) shows true signatures of single-molecule magnet behavior in the absence of a dc field. In addition, the mononuclear Dy and Tb complexes [{(thf) 2 Li(NtBu) 2 S(tBuN) 2 LnCl 2 (thf) 2 ] (2b,c) show slow magnetic relaxation under applied dc fields.

show abstract

Tetraimido Sulfuric Acid H₂S(NtBu)₄—Valence Isoelectronic to H₂SO₄

Cited by 13 publications

References 50 publications

Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets

Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets

Polyanionic Imido‐P(V) Ligands: From Transition Metal Complexes to Coordination Driven Self‐Assemblies

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes

Contact Info

Product

Resources

About

Tetraimido Sulfuric Acid H2S(NtBu)4—Valence Isoelectronic to H2SO4

Cited by 13 publications

References 50 publications

Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets

Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets

Polyanionic Imido‐P(V) Ligands: From Transition Metal Complexes to Coordination Driven Self‐Assemblies

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)42− Complexes

Contact Info

Product

Resources

About

Tetraimido Sulfuric Acid H₂S(NtBu)₄—Valence Isoelectronic to H₂SO₄

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes