Reactions of tris(2-pyridyl)phosphines and tris(2-pyridyl)phosphine oxides with some electrophiles

Uchida, Yuzuru; Kajita, Kimihiko Matsuoka Ryuji; Kawasaki, Yoshikane; Ōae, Shigeru

doi:10.1002/(sici)1098-1071(1997)8:5<439::aid-hc9>3.0.co;2-3

Cited by 5 publications

(4 citation statements)

References 6 publications

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“…Compound 1 is seemingly indefinitely air‐ and moisture‐stable and is readily isolated as colourless crystals in 36 % yield after crystallisation from dichloromethane/hexane, without the need for column chromatography. In addition to analytical and spectroscopic data (see Experimental Section), the single‐crystal X‐ray structure (Figure b) does not show Mg 2+ coordination to 1 in its synthesis, as can commonly occur in this area . This is important because the presence of a contaminant metal ion can be a complication in ligand transfer to other metals.…”

Section: Resultsmentioning

confidence: 94%

“…[2] Severin and co-workersh ave overcome this tendency by incorporatinga dditional steric groups into bis(3-pyridyl) Fe clathrochelate ligandst op roduce Pd 6 L 12 12 + cages, [2] and have found that tuningt he sterics alters the size of the cage. [3] This metalloligand strategy for the construction of heterometallic supramolecular architectures has been successfully enacted for av ariety of mixed transition metals ystems, for example, Fe/Pd, [2,[4][5][6] Fe/Ru, [7] Fe/Co, [8,9] Co/ Mn [5] and Ru/Pd. [10,11] However,t he use of main group metalloligands to createmixed main group/transitionmetal heterometallic systems is rare.…”

Section: Introductionmentioning

confidence: 99%

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A Tris(3‐pyridyl)stannane as a Building Block for Heterobimetallic Coordination Polymers and Supramolecular Cages

Yang

Plajer

García-Romero

et al. 2019

Chemistry A European J

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The systematic assembly of supramolecular arrangements is a persistent challenge in modern coordination chemistry, especially where further aspects of complexity are concerned, as in the case of large molecular mixed‐metal arrangements. One targeted approach to such heterometallic complexes is to engineer metal‐based donor ligands of the correct geometry to build 3D arrangements upon coordination to other metals. This simple idea has, however, only rarely been applied to main group metal‐based ligand systems. Here, we show that the new, bench‐stable tris(3‐pyridyl)stannane ligand PhSn(3‐Py)3 (3‐Py=3‐pyridyl) provides simple access to a range of heterometallic SnIV/transition metal complexes, and that the presence of weakly coordinating counter anions can be used to build discrete molecular arrangements involving anion encapsulation. This work therefore provides a building strategy in this area, which parallels that of supramolecular transition metal chemistry.

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Section: Resultsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

A Tris(3‐pyridyl)stannane as a Building Block for Heterobimetallic Coordination Polymers and Supramolecular Cages

Yang

Plajer

García-Romero

et al. 2019

Chemistry A European J

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“…The ligand was prepared using a modified procedure from the literature. 33 2,6-Dibromopyridine (4.74 g, 20 mmol) was dissolved in 40 mL of diethyl ether and cooled down to −60 °C. To this white slurry a solution of n BuLi (12.5 ml, 20 mmol, 1.6 M in n-hexane) was added dropwise.…”

Section: Methodsmentioning

confidence: 99%

Sterically-constrained tripodal phosphorus-bridged tris-pyridyl ligands

et al. 2016

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Introducing substituents into the 6-position of the 2-pyridyl rings of neutral tris-pyridyl phosphanes of the type P(2-py')3 (where 2-py' is a substituted 2-pyridyl ring), has a marked impact on their coordination of transition metal ions, as revealed in the current study. Whereas the unsubstituted phosphorus-bridged tris-pyridyl ligand P(2-py)3 (1) forms the sandwich cation [{P(py)3}2Fe](2+) (4) with iron(II), coordinating via all of the donor nitrogen atoms, the reaction of the methyl-substituted counterpart P(6-Me-2-py)3 (2) and FeCl2 results in the half-sandwich arrangement [{P(6-Me-2-py)3}FeCl2]·toluene (5·toluene), in which only two N-atoms of the ligand coordinate to the metal. A similar half-sandwich type complex, [{P(6-Me-2-py)3}FeCl(OTf)]·2THF (6·2THF), is obtained from reaction of 2 with Fe(OTf)2 in the presence of LiCl, only now with all three of the N-atoms of the ligand coordinated to Fe(II). The formation of a half-rather than full-sandwich complex 2 with suggests that steric clashing of the Me groups prevents the formation of sandwich-type arrangements. The reaction of [Cu(MeCN)4]PF6 with P(6-Me-2-py) (2) gives the complex [(MeCN)3Cu{P(6-Me-2-py)3}Cu(MeCN)](PF6)2 (7), in which two Cu(I) atoms are coordinated by the bridgehead P-atom and by the three N-atoms of the tris-pyridyl ligand (a unique coordination mode in this area). Overall, the results indicate that 6-Me substitution results in a promising 6-electron capping ligand for organometallic synthesis and catalysis.

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“…[84][85][86] In the second step, the oxidized ligand tpypo L1 was synthesized according to a previously published method, which was slightly modified. In the literature, [87][88][89][90] hydrogen peroxide solution was used to oxidize tpyp, whereas in our procedure tBuOOH (80% in DTBP) was used. The other two ligands tpyps L2 and tpypse L3 could be easily prepared by refluxing tpyp with elemental sulfur or gray selenium in toluene.…”

Section: Synthesis Of the Ligandsmentioning

confidence: 99%

A new class of luminescent Cu(i) complexes with tripodal ligands – TADF emitters for the yellow to red color range

et al. 2015

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A new class of emissive and neutral Cu(I) compounds with tripodal ligands is presented. The complexes were characterized chemically, computationally, and photophysically. Under ambient conditions, the powders of the compounds exhibit yellow to red emission with quantum yields ranging from about 5% to 35%. The emission represents a thermally activated delayed fluorescence (TADF) combined with a short-lived phosphorescence which represents a rare situation and is a consequence of high spin-orbit coupling (SOC). In the series of the investigated compounds the non-radiative rates increase with decreasing emission energy according to the energy gap law while the radiative rate is almost constant. Furthermore, a well-fit linear dependence between the experimental emission energies and the transition energies calculated by DFT and TD-DFT methods could be established, thus supporting the applicability of these computational methods also to Cu(I) complexes.

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Reactions of tris(2-pyridyl)phosphines and tris(2-pyridyl)phosphine oxides with some electrophiles

Cited by 5 publications

References 6 publications

A Tris(3‐pyridyl)stannane as a Building Block for Heterobimetallic Coordination Polymers and Supramolecular Cages

A Tris(3‐pyridyl)stannane as a Building Block for Heterobimetallic Coordination Polymers and Supramolecular Cages

Sterically-constrained tripodal phosphorus-bridged tris-pyridyl ligands

A new class of luminescent Cu(i) complexes with tripodal ligands – TADF emitters for the yellow to red color range

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