Synthesis and Properties of Lanthanum- Pyrene Complexes—Structure of [(Cp*La)3(μ-Cl)3(thf)(μ-η2:η6:η6-C16H10)], the First Complex with a Pyrene Trianion

Thiele, K.‐H.; Bambirra, Sergio; Sieler, Joachim; Yelonek, Svea

doi:10.1002/(sici)1521-3773(19981102)37:20<2886::aid-anie2886>3.0.co;2-g

Cited by 31 publications

(15 citation statements)

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“…The bridging oxygen has a distance of 2.471(1) Å for La(1)-O(4′) and a long-range interaction of 2.904(1) Å for La(1)-O(4). The La-(C 5 Me 5 ) distance is 2.490 Å and can be compared to other mono-(C 5 Me 5 ) complexes of lanthanum: 2.503 Å for (C 5 Me 5 )La(AlMe 4 ) 2 , 58 2.517, 2.537, and 2.541 Å for {[C 5 Me 5 )La] 3 (µ-Cl) 3 (thf)(µ-η 2 :η 6 :η 6 -C 16 H 10 )}, 59 2.528 and 2.534 Å for (C 5 Me 5 )La[CH(SiMe 3 ) 2 ] 2 , 60,61 and 2.559 Å for (C 5 Me 5 )La[CH(SiMe 3 ) 2 ] 2 (THF). 61 Reaction of (C 5 Me 4 H) 3 Ln with CO 2 (Ln ) La, Nd, Sm, Gd).…”

Section: Resultsmentioning

confidence: 94%

“…The bridging oxygen has a distance of 2.471(1) Å for La(1)−O(4‘) and a long-range interaction of 2.904(1) Å for La(1)−O(4). The La−(C 5 Me 5 ) distance is 2.490 Å and can be compared to other mono-(C 5 Me 5 ) complexes of lanthanum: 2.503 Å for (C 5 Me 5 )La(AlMe 4 ) 2 , 2.517, 2.537, and 2.541 Å for {[C 5 Me 5 )La] 3 (μ-Cl) 3 (thf)(μ-η 2 :η 6 :η 6 -C 16 H 10 )}, 2.528 and 2.534 Å for (C 5 Me 5 )La[CH(SiMe 3 ) 2 ] 2 , , and 2.559 Å for (C 5 Me 5 )La[CH(SiMe 3 ) 2 ] 2 (THF) 4 Selected Bond Distances (Å) and Angles (deg) for (C 5 Me 5 )La(μ-η 1 :η 2 -O 2 CC 5 Me 5 )(μ-η 1 :η 1 -O 2 CC 5 Me 5 )] 2 , 2 La(1)−Cnt a 2.490 Cnt−La(1)−O(1) 109.4 La(1)−O(1) 2.4202(11) Cnt−La(1)−O(2‘) 110.0 La(1)−O(2‘) 2.4363(11) Cnt−La(1)−O(3) 100.8 La(1)−O(3) 2.4542(12) Cnt−La(1)−O(4‘) 123.4 La(1)−O(4‘) 2.4715(11) La(1)−O(4)−La(1‘) 91.73(3) La(1)−O(4) 2.9073(11) O(3)−La(1)−O(4‘) 99.90(4) La(1)−La(1‘) 3.8700(4) a Cnt is C(1)−C(5). …”

Section: Resultsmentioning

confidence: 94%

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Facile Insertion of CO₂ into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C₅Me₄RCO₂)^- Carboxylate Ligands (R = H, Me)

et al. 2007

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Recent efforts to extend the reduction chemistry of LnZ 3 /M and LnZ 2 Z′/M (Ln ) lanthanide; Z ) C 5 Me 5 , C 5 Me 4 H; Z′ ) BPh 4 , Cl; M ) alkali metal) to substrates beyond N 2 have identified unexpectedly facile insertion of CO 2 into lanthanide cyclopentadienyl linkages to make carboxylate ligands. The insertion was initially identified in [(C 5 Me 4 H)La(THF)] 3 (µ-η 1 :η 1 -O 2 CC 5 Me 4 H) 3 (µ 3 -η 2 :η 2 :η 2 -CO 3 )(µ 3 -Cl), 1, a product of a (C 5 Me 4 H) 3 La/Na/CO 2 reaction in the presence of chloride. In this case, both insertion and reduction of CO 2 to carbonate was observed. A [(C 5 Me 5 ) 2 La][(µ-Ph) 2 BPh 2 ]/KC 8 /CO 2 reaction also provided a CO 2 insertion product, [(C 5 Me 5 )La(µ-η 1 :η 1 -O 2 CC 5 Me 5 )(µ-η 1 :η 2 -O 2 CC 5 Me 5 )] 2 , 2, but in this case a CO 2 reduction product was not identified. CO 2 insertion also occurs in the absence of an alkali metal. Hence, the (C 5 -Me 4 H) 3 Ln complexes (Ln ) La, Nd, Sm, Gd) react with CO 2 to form mixtures of tetramethylcyclopentadienyl carboxylate products. In the La complex, single crystals of {[(C 5 Me 4 H) 2 La](µ-η 1 :η 1 -O 2 CC 5 -Me 4 H)} 2 , 3, could be isolated and structurally characterized. Crystallographic characterization of a rare example of a tetramethylcyclopentadienyl lanthanide ate salt, [(µ-C 5 Me 4 H)(C 5 Me 4 H)LaCl(µ-Cl)K(18crown-6)] n , 4, was also obtained as part of this study, and it was found to have a chain structure in the solid state involving bridging methyl groups as well as bridging chloride ligands.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 94%

Facile Insertion of CO₂ into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C₅Me₄RCO₂)^- Carboxylate Ligands (R = H, Me)

et al. 2007

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“…An analogous tendency has been described for several lanthanide compounds with dianions of nitrogen con taining heterocyclic compounds. 8,9,28 Behavior of the complexes in solution. To make sure that the short contacts between the ortho positions of the Ph groups and the Lu cation, which were revealed by X ray diffraction, are retained in solution, we studied complexes 1, 2, and 4 by NMR spectroscopy.…”

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confidence: 99%

Lutetium complexes with tetraphenylethylene dianion. Synthesis and structure

et al. 2004

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“…Overall, the samarium atoms span the base of a trigonal bipyramid, with the two μ 3 -bridging iodo ligands representing the vertices of the pyramids and the three μ 2 -bridging iodo ligands engaging in an almost planar six-membered metallacycle. Such trimetallic units [Ln 3 (μ 2 -X) 3 (μ 3 -X) 2 ] are quite common in rare-earth-metal coordination chemistry, − and the most relevant examples comprise [Cp 3 Yb 3 (μ 3 -Cl) 2 (μ-Cl) 3 (THF) 3 ][Cp 6 Yb 6 (μ 6 -Cl)(μ-Cl) 12 ], [Y 3 (O t Bu) 3 (X)(μ 2 -O t Bu) 3 (μ 3 -O t Bu)(μ 3 -Cl)(THF) 2 ] (X = Cl, O t Bu), , [Er 3 (OAr OMe ) 4 (μ 2 -F) 3 (μ 3 -F) 2 (THF) 4 ], [L 3 Gd 3 Cl 5 ][B(C 6 F 5 ) 4 ] (with L being a β-diketiminato ligand), and the very similar samarium complex [{Cp*Sm(THF)} 3 (μ-Cl) 5 ][BPh 4 ], which was obtained by an oxidation reaction involving Cp*Sm[BPh 4 ] and tert -butyl chloride (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Donor-Solvent-Dependent Cluster Formation of (C₅Me₅)SmI₂(THF)_x-Type Half-Sandwich Complexes

et al. 2016

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In this study, we demonstrate the structural variety of the Cp*SmI y system with respect to the amount of donor molecules (THF) present. The reaction of SmI2(THF)2 with 0.5 equiv of bis(pentamethylcyclopentadienyl)lead(II), PbCp*2, in THF gives the highly solvated monomeric complex Cp*SmI2(THF)3, when crystallized from THF. The same reaction performed in n-hexane followed by crystallization from toluene gave the partially solvated trimetallic complex [Cp*3Sm3I(μ2-I)3(μ3-I)2(THF)2]. Recrystallization of the Sm3 cluster from either C6D6 at ambient temperature or toluene at −40 °C produced the tetrametallic complex [Cp*4Sm4I(μ2-I)4(μ3-I)2(μ4-I)(THF)]. Reaction of SmI2, obtained via treatment of SmI2(THF)2 with excess AlEt3 in n-pentane, with 0.5 equiv of PbCp*2 in toluene led to the donor-free mixed-valent pentametallic complex [Cp*5Sm5(μ2-I)4(μ3-I)4(μ5-I)]. All compounds were characterized by single-crystal X-ray structure analysis.

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Synthesis and Properties of Lanthanum- Pyrene Complexes—Structure of [(Cp*La)3(μ-Cl)3(thf)(μ-η2:η6:η6-C16H10)], the First Complex with a Pyrene Trianion

Cited by 31 publications

References 6 publications

Facile Insertion of CO₂ into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C₅Me₄RCO₂)^- Carboxylate Ligands (R = H, Me)

Facile Insertion of CO₂ into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C₅Me₄RCO₂)^- Carboxylate Ligands (R = H, Me)

Lutetium complexes with tetraphenylethylene dianion. Synthesis and structure

Donor-Solvent-Dependent Cluster Formation of (C₅Me₅)SmI₂(THF)_x-Type Half-Sandwich Complexes

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Synthesis and Properties of Lanthanum- Pyrene Complexes—Structure of [(Cp*La)3(μ-Cl)3(thf)(μ-η2:η6:η6-C16H10)], the First Complex with a Pyrene Trianion

Cited by 31 publications

References 6 publications

Facile Insertion of CO2 into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C5Me4RCO2)- Carboxylate Ligands (R = H, Me)

Facile Insertion of CO2 into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C5Me4RCO2)- Carboxylate Ligands (R = H, Me)

Lutetium complexes with tetraphenylethylene dianion. Synthesis and structure

Donor-Solvent-Dependent Cluster Formation of (C5Me5)SmI2(THF)x-Type Half-Sandwich Complexes

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Facile Insertion of CO₂ into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C₅Me₄RCO₂)^- Carboxylate Ligands (R = H, Me)

Facile Insertion of CO₂ into Tetra- and Pentamethylcyclopentadienyl Lanthanide Moieties To Form (C₅Me₄RCO₂)^- Carboxylate Ligands (R = H, Me)

Donor-Solvent-Dependent Cluster Formation of (C₅Me₅)SmI₂(THF)_x-Type Half-Sandwich Complexes