Coordination Abilities of Di‐2‐picolylphenylphosphane Judged on the Basis of Charge Density Investigations

Objartel, Ina; Leusser, Dirk; Engelhardt, Felix; Herbst‐Irmer, Regine

doi:10.1002/zaac.201300092

Cited by 5 publications

(2 citation statements)

References 33 publications

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“…This is most likely caused by deprotonation of the methylene moiety in quickly formed ClPhPCH 2 (bipy) and PhP(CH 2 (bipy)) 2 by LiCH 2 (bipy), which is still present in the reaction mixture. A similar behavior is observed for the corresponding picolyl phosphines, which can also be deprotonated with lithium organyls …”

Section: Resultssupporting

confidence: 73%

“…As imilarb ehavior is observed for the corresponding picolyl phosphines, which can also be deprotonatedwithlithium organyls. [34][35][36] However,t he ligand PN4 could be successfully prepared through chlorotrimethylsilane elimination. Braunstein et al were able to preparet he related ligand bis(2-picolyl)phenylphosphine by reacting purified 2-[(trimethylsilyl)methyl]pyridine with dichlorophenylphosphine.…”

Section: Resultsmentioning

confidence: 99%

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Bis(6‐methylene‐2,2′‐bipyridine)phenylphosphine—A Flexible Ligand for the Construction of Trinuclear Coinage‐Metal Complexes

Schäfer

Gamer

Lebedkin

et al. 2017

Chemistry A European J

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Bis-(6-methylene-2,2'-bipyridine)phenylphosphine (PN4) was designed as a tailor-made ligand with different metal binding sites (N and P) to support metallophilic interactions between the different coinage metals, as these are far less common than homometallic interactions, typically between gold(I) ions. Furthermore, the phosphorus(V)sulfide derivative of PN4 was synthesized to get additional structural information in the solid state. Two mononuclear gold complexes [(PN4)AuCl] and [(PN4) Au]ClO were synthesized first. Then, the two hetero trimetallic gold complexes [(PN4) AuAg ](OTf) (Tf=triflate) and [(PN4) AuCu ](OTf) were synthesized by selectively filling the bipyridine coordination compartments with the lighter coinage metals. For comparison two trinuclear silver complexes, that is, [(PN4) Ag ]OTf and [(PN4)(py) Ag (μ-Cl)(μ -Cl)]ClO (py=pyridine) were prepared. All compounds were fully characterized including single-crystal X-ray diffraction, N, F and Ag NMR spectroscopy. The photophysical properties of the new compounds were determined in the solid state. These revealed a different behavior between the Au-Cu and Au-Ag/Ag-Ag compounds. [(PN4) AuAg ](OTf) was found to be the brightest emitter. Time-dependent density functional calculations were performed to illuminate the differences in the photophysical properties.

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Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Bis(6‐methylene‐2,2′‐bipyridine)phenylphosphine—A Flexible Ligand for the Construction of Trinuclear Coinage‐Metal Complexes

Schäfer

Gamer

Lebedkin

et al. 2017

Chemistry A European J

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Imido-pyridine Ti(iv) compounds: synthesis of unusual imido–amido heterobimetallic derivatives

et al. 2015

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The reaction of lithiated picolines and [TiCl3(η(5)-C5Me5)] leads to several bridging or terminal imido compounds, each of which can be selectively formed by controlling the stoichiometry and temperature. Specifically, the dinuclear imido-bridged [TiCl(η(5)-C5Me5)(μ-NR)]2 (1a, NR = 2-imido-3-picoline; 1b, NR = 2-imido-5-picoline) species and the unusual Ti-Li imido-amido heterobimetallic complex [{Li(THF)}{Ti(η(5)-C5Me5)(NR)(NHR)2}] (2a, NR = 2-imido-3-picoline; 2b, NR = 2-imido-5-picoline) were isolated. Compounds 2 are in effect the first structurally characterized examples of titanium(IV) coordinated to terminal imido-pyridines. DFT-D calculations for 2a denote a multiple bond character between titanium and the imido ligand and a strong polarization of the electron density by the alkali cation in spite of the lack of intermetallic bonding.

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Multidentate 2-pyridyl-phosphine ligands – towards ligand tuning and chirality

et al. 2017

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In the current work a range of multidentate pyridyl-phosphine ligands are synthesised with tuneable electronic and steric character, through the incorporation of a variety of alcohols into (amino)pyridyl-phosphine frameworks. The stoichiometric reactions of compounds of the type (RN)P(2-py) (2-py = 2-pyridyl) with alkyl as well as aryl alcohols result in the formation of (alkoxy)pyridyl-phosphines (RO)P(2-py) (R = Me, 2-Bu, Ph). This synthetic procedure also allows the introduction of enantiomerically pure alcohols, like (R)-(-)-2-BuOH and (S)-(+)-2-BuOH, and as such provides a very convenient two-step route to chiral multidentate pyridyl-phosphine ligand sets. Using the bis-amino-phosphine (EtN)P(2-py), the stepwise introduction of alcohols enables the synthesis of racemic alkoxy-amino-phosphines (RN)(RO)P(2-py), as well as alkoxy-phosphines (RO)P(2-py) and therefore offers easy access to a library of different pyridyl-phosphine ligands. Coordination studies of the (amino)pyridyl-phosphines and (alkoxy)pyridyl-phosphines with copper(i) reveal that ligands with two N donor atoms form dimeric arrangements, while (PhO)P(2-py), in-corporating only one N donor atom, shows completely different coordination behaviour.

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Coordination Abilities of Di‐2‐picolylphenylphosphane Judged on the Basis of Charge Density Investigations

Cited by 5 publications

References 33 publications

Bis(6‐methylene‐2,2′‐bipyridine)phenylphosphine—A Flexible Ligand for the Construction of Trinuclear Coinage‐Metal Complexes

Bis(6‐methylene‐2,2′‐bipyridine)phenylphosphine—A Flexible Ligand for the Construction of Trinuclear Coinage‐Metal Complexes

Imido-pyridine Ti(iv) compounds: synthesis of unusual imido–amido heterobimetallic derivatives

Multidentate 2-pyridyl-phosphine ligands – towards ligand tuning and chirality

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