2,4,6-Tris(trifluormethyl)phenyl und 2,-4,6-Tris(trifluormethyl)-dithiobenzoat als Liganden in Cobalt(II)-und Nickel(II)-Verbindungen

Belay, M. T.; Edelmann, Frank T.

doi:10.1016/0022-328x(94)84122-5

Cited by 21 publications

(4 citation statements)

References 15 publications

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“…The presence of ancillary ligands seems important in obtaining well-defined (Fmes)palladium complexes, since the reaction of PdCl 2 with excess of Li(Fmes) for 24 h at 40 °C gave only a very small amount of an orange oil, which was a complex mixture of species by 19 F NMR. This is in contrast with the ready isolation of [Ni(Fmes) 2 ] and [Co(Fmes) 2 ], which have been described recently . It is well-known that low-coordinate complexes are more easily obtained for smaller metals.…”

Section: Resultsmentioning

confidence: 80%

“…The stability of these complexes is attributed, in addition to the above mentioned factors common to fluoroaryls, to the steric bulk of the ligand and to the possibility of short metal−fluorine interactions involving the ortho -CF 3 groups. These properties should make the 2,4,6-tris(trifluoromethyl)phenyl group an interesting ligand also for transition metals, but so far there are only two reports on its coordination to middle transition metals: It is mentioned in a review that Herrmann's group has synthesized Re(Fmes)O 3 , and a recent communication has appeared reporting the syntheses of Co(Fmes) 2 and Ni(Fmes) 2 , although no X-ray structures have been reported.…”

Section: Introductionmentioning

confidence: 99%

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(2,4,6-Tris(trifluoromethyl)phenyl)palladium(II) Complexes

Bartolomé¹,

Espinet²,

Villafañe³

et al. 1996

Organometallics

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Complexes containing one or two Fmes ligands (Fmes = 2,4,6-tris(trifluoromethyl)phenyl = nonafluoromesityl) either trans or cis are obtained by treating palladium(II) chloro complexes with Li(Fmes): trans-[PdCl2L2] (L = tetrahydrothiophene (tht), PPh3) lead to trans-[Pd(Fmes)ClL2] (L = tht, PPh3) or trans-[Pd(Fmes)2L2] (L = tht); [PdCl2(L-L)] (L-L = 1,5-cyclooctadiene, 2,2‘-bipyridine) give [Pd(Fmes)Cl(L-L)] (L-L = COD, bipy) or [Pd(Fmes)2(bipy)]. The structures of two complexes containing two Fmes ligands in trans and cis arrangement, trans-[Pd(Fmes)2(tht)2] (2) and [Pd(Fmes)2(bipy)] (6), respectively, have been determined by X-ray diffraction. In spite of the severe steric congestion the complexes are four coordinated. Distortions due to the bulkiness of the ortho substituents and short Pd···F3C-ortho distances are observed. The high degree of steric crowding is also responsible for slow rotation around the Pd−P bonds in the complex trans-[Pd(Fmes)Cl(PPh3)2]. ΔG ⧧ associated with this motion is 12.8 kcal mol-1, one of the highest values reported so far for rotation around M−PPh3 bonds. Complexes 2 and 6 are redox inactive by cyclic voltammetry in the range −1.8 to +1.8 V.

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Section: Resultsmentioning

confidence: 80%

Section: Introductionmentioning

confidence: 99%

(2,4,6-Tris(trifluoromethyl)phenyl)palladium(II) Complexes

Bartolomé¹,

Espinet²,

Villafañe³

et al. 1996

Organometallics

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“…Additionally, we hypothesized that the relatively bulky ortho -CF 3 substituents would impart further kinetic stability to the U–C bonds. In fact, Fmes is known for its ability to stabilize unusual fragments, especially those with low coordination numbers and unstable oxidation states. − For example, the Fmes ligand was used to stabilize the first bis(aryl) plumbylene [Pb(Fmes) 2 ] and the first monomeric bis(aryl) stannylene [Sn(Fmes) 2 ]. , Fmes was also used to stabilize [(Fmes) 2 MM(Fmes) 2 ] (M = Ga, In), which represent early examples of complexes with stable In–In and Ga–Ga bonds …”

Section: Introductionmentioning

confidence: 99%

Quantifying Actinide–Carbon Bond Covalency in a Uranyl–Aryl Complex Utilizing Solution ¹³C NMR Spectroscopy

Ordoñez,

Yu,

et al. 2023

Inorg. Chem.

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Reaction of [UO 2 Cl 2 (THF) 2 ] 2 with in situ generated LiFmes (FmesH = 1,3,5-(CF 3 ) 3 C 6 H 3 ) in Et 2 O resulted in the formation of the uranyl aryl complexes [Li(THF) 3 ][UO 2 (Fmes) 3 ] ([Li(THF) 3 ][1]) and [Li-(Et 2 O) 3 (THF)][UO 2 (Fmes) 3 ] ([Li(Et 2 O) 3 (THF)][1]) in good to moderate yields after crystallization from hexanes and Et 2 O, respectively. Both complexes were characterized by X-ray crystallography and NMR spectroscopy. DFT calculations reveal that the C ispo resonance in [1] − exhibits a deshielding of 51 ppm from spin− orbit coupling effects originating at uranium, which indicates an appreciable covalency in the U−C bonding interaction.

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“…These properties have made Fmes an interesting ligand for main-group elements, where it stabilizes low-valent or low-coordinated complexes. Thus, Fmes complexes are known for group 13, group 14, and Bi and also for group 12 elements, whereas transition-metal complexes have been reported for V, Cr, Mo, Re, Co, Ni, and Pd . The only group 11 derivative reported so far is Cu(Fmes), which was not isolated as a solid 9a…”

Section: Introductionmentioning

confidence: 99%

[2,4,6-Tris(trifluoromethyl)phenyl]gold(I) and -gold(III) Complexes

et al. 1999

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The complex [Au(Fmes)(tht)] (Fmes = 2,4,6-tris(trifluoromethyl)phenyl or nonafluoromesityl; tht = tetrahydrothiophene) was obtained by reaction of [AuCl(tht)] and Li(Fmes). Monoarylated complexes are readily obtained when the tht ligand is displaced by other neutral ligands, giving [Au(Fmes)L] (L = PPh3, P(o-tol)3, 2,6-lutidine) or [Au2(Fmes)2(μ-bipy)] (bipy = 2,2‘-bipyridyl), the latter containing a bridging bipy ligand. tht can also be displaced by halides to give the gold anionic complexes NBu4[Au(Fmes)X] (X = Cl, Br, I). [Au(Fmes)(NCMe)] is obtained from the latter by treatment with TlBF4 in the presence of MeCN. The bis-arylated complexes NR4[Au(Fmes)2] (R = Et, Bu) were obtained by treatment of NR4[AuBr2] with excess Li(Fmes). They react with AgBF4 and 4-methylpyridine to give [Ag(4-Mepy)2][Au(Fmes)2]. Oxidative addition of halogens to the monoarylated NBu4[Au(Fmes)X] and the bis-arylated NR4[Au(Fmes)2] gives the gold(III) complexes NBu4[Au(Fmes)X3] and NR4[trans-Au(Fmes)2X2], respectively. The structures of the bis-arylated gold(I) and -(III) complexes NBu4[Au(Fmes)2] and NEt4[trans-Au(Fmes)2I2] were determined by X-ray diffraction. An analysis of nonbonded distances and torsion angles suggests that steric repulsion of neighboring CF3 groups is reduced by mutual rotation of the Fmes rings in the former complex but by rotation of the CF3 groups themselves in the latter (in which the Fmes rings are exactly coplanar).

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2,4,6-Tris(trifluormethyl)phenyl und 2,-4,6-Tris(trifluormethyl)-dithiobenzoat als Liganden in Cobalt(II)-und Nickel(II)-Verbindungen

Cited by 21 publications

References 15 publications

(2,4,6-Tris(trifluoromethyl)phenyl)palladium(II) Complexes

(2,4,6-Tris(trifluoromethyl)phenyl)palladium(II) Complexes

Quantifying Actinide–Carbon Bond Covalency in a Uranyl–Aryl Complex Utilizing Solution ¹³C NMR Spectroscopy

[2,4,6-Tris(trifluoromethyl)phenyl]gold(I) and -gold(III) Complexes

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2,4,6-Tris(trifluormethyl)phenyl und 2,-4,6-Tris(trifluormethyl)-dithiobenzoat als Liganden in Cobalt(II)-und Nickel(II)-Verbindungen

Cited by 21 publications

References 15 publications

(2,4,6-Tris(trifluoromethyl)phenyl)palladium(II) Complexes

(2,4,6-Tris(trifluoromethyl)phenyl)palladium(II) Complexes

Quantifying Actinide–Carbon Bond Covalency in a Uranyl–Aryl Complex Utilizing Solution 13C NMR Spectroscopy

[2,4,6-Tris(trifluoromethyl)phenyl]gold(I) and -gold(III) Complexes

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Quantifying Actinide–Carbon Bond Covalency in a Uranyl–Aryl Complex Utilizing Solution ¹³C NMR Spectroscopy