1,3-Bis(trimethylsilyl)-2-phenyl-1-aza-3-phosphapropenide Anions as Bidentate Ligands for the Alkaline Earth Metals Magnesium, Calcium, Strontium, and Barium

Westerhausen, Matthias; Digeser, Matthias H.; Schwarz, W.

doi:10.1021/ic960887t

Cited by 44 publications

(11 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[20d, 21] Herein we report the synthesis of nitrilium triflates and their reactivity toward primary phosphanes, [22] which allows the facile synthesis of C, D, and bis(imino)phosphanes.…”

mentioning

confidence: 99%

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

et al. 2014

View full text Add to dashboard Cite

Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of a novel class of 1,3-P,N ligands as demonstrated for the reaction with primary phosphanes. This procedure allows variation of all substituents. X-ray crystal structures are reported for nitrilium ions, phosphaamidines, and three phosphaamidinate complexes. The lithium phosphaamidinate is N coordinated and its reaction with [AuCl(tht)] (tht = tetrahydrothiophene) gives a unique P-bridged gold trimer, while a P,N-bidentate complex results from [{RhCl(cod)}2]. The nitrilium ion methodology allows extension of the 1,3-P,N motive to bis(imino)phosphanes, which are the neutral phosphorus analogues of the valuable β-diketiminate ligand.

show abstract

“…[20d, 21] Herein we report the synthesis of nitrilium triflates and their reactivity toward primary phosphanes, [22] which allows the facile synthesis of C, D, and bis(imino)phosphanes.…”

mentioning

confidence: 99%

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

et al. 2014

View full text Add to dashboard Cite

show abstract

“…Verglichen mit 3 sind in 4 die Ca‐O(Ligand)‐Bindungen etwas kürzer, die Ca‐C‐Bindungen etwas länger. Die Ca‐P‐Bindungslänge von 2.986(3) Å in 4 kann nur mit denen im Calcium‐Diphosphanylmethanidkomplex [Ca{(PMe 2 ) 2 C(SiMe 3 )} 2 (thf) 3 ] ( d (Ca‐P)=3.043 Å, Mittelwert) verglichen werden, dem einzigen anderen Fall einer kristallographisch charakterisierten Verbindung mit Ca‐PR 3 ‐Bindungen 22, 23. Mit einer Winkelsumme von 333.0° (ohne Calcium) ist auch das carbanionoide Kohlenstoffatom C1 in 4 pyramidalisiert.…”

Section: Methodsunclassified

Tagungskalender

2008

Nachr Chem

View full text Add to dashboard Cite

Harte und weiche Donorzentren (O bzw. P und C) weisen die mehrzähnigen, sauerstoffsubstituierten anionischen Phosphanliganden I und II auf, die damit offenbar besonders gut geeignet für die Komplexierung von Calcium sind. Mit diesen mono‐ bzw. dianionischen Liganden gelang die Synthese neuartiger Organocalciumverbindungen ohne Cyclopentadienylliganden: eines Trialkylcalcates(II) bzw. der ersten Organocalciumverbindung mit einer Heterocubanstruktur. Ph′=p‐Tolyl.

show abstract

“…Such elements include the alkaline‐earth (Ae) and boron‐group (Bg) elements, and beryllium, magnesium, calcium, boron, aluminum, and gallium are abundant . Catalysts based on Ae and Bg elements are therefore more accessible than those containing heavy transition metals and can be used to promote reactions such as heterolytic H 2 cleavage, and the formation of carbon–carbon and carbon–heteroatom bonds . The development of catalysts based on Ae and Bg elements is therefore an emerging research theme …”

Section: Introductionmentioning

confidence: 99%

Benchmark study of popular density functionals for calculating binding energies of three‐center two‐electron bonds

Cui

Ding

et al. 2018

J Comput Chem

View full text Add to dashboard Cite

Density functional theory (DFT) can be used to study the three‐center two‐electron (3c2e) bonding mode, which is universal in catalysts containing alkaline‐earth (Ae) and boron‐group (Bg) elements. However, because of the delocalization pattern of the 3c2e bond, the wavefunction cannot be accurately described by DFT methods. The calculated energies of Ae and Bg catalysts therefore fluctuate greatly when different functionals are used, largely because of inconsistent DFT‐calculated binding energies of 3c2e bonds. Nevertheless, with the development of supercomputers and theoretical calculation software, the DFT method is becoming increasingly popular for studying Ae and Bg catalysts. In this study, we compared the performances of 21 functionals with the high‐level composite G3B3 method in calculations for the binding energies of 3c2e bonds. Several frequently used post‐Hartree–Fock methods were also tested. The calculation results indicate that the M06‐2X, MN12‐L, and MN15 functionals give consistent and reliable binding energies for common 3c2e bonds. © 2018 Wiley Periodicals, Inc.

show abstract

1,3-Bis(trimethylsilyl)-2-phenyl-1-aza-3-phosphapropenide Anions as Bidentate Ligands for the Alkaline Earth Metals Magnesium, Calcium, Strontium, and Barium

Cited by 44 publications

References 15 publications

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

Tagungskalender

Benchmark study of popular density functionals for calculating binding energies of three‐center two‐electron bonds

Contact Info

Product

Resources

About