Half-sandwich halolanthanacarboranes of the “carbons adjacent” C2B4-carborane ligand systems: important synthons for new polyhedral cage constructs

Wang, Jianhui; Zheng, Chong; Li, Ang; Allard, Christina L.; Smith, Joanna L.; Arikatla, Gauthami; Maguire, John A.; Hosmane, Narayan S.

doi:10.1016/j.inoche.2004.07.015

Cited by 9 publications

(9 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The Y−cage atom distances range from 2.653(5) to 2.729(4) Å with an average value of 2.627(5) Å. This measured value is significantly shorter than the corresponding values observed in 3 and 4 , but is comparable to the corresponding value of 2.715(20) Å found in {[{ η 5 -(Me 3 Si) 2 C 2 B 4 H 4 } 2 YCl(THF)]Li(THF)}{Li(THF) 4 } 5a. The terminal Y−Cl distance of 2.561(1) Å is the same as that of 2.561(1) Å found in 4 .…”

Section: Resultssupporting

confidence: 58%

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C₂B₉ and C₂B₁₀ Systems

2005

View full text Add to dashboard Cite

Reaction of 1-Me2NCH2CH2-1,2-C2B10H11 (1) with excess Na metal in THF, followed by treatment with 1 equiv of YCl3, afforded [η 1:η 6-(Me2NCH2CH2)C2B10H11]YCl(THF)3 (2), which contains a terminal Y−Cl bond. Recrystallization of 2 from MeCN/toluene gave [η 1:η 6-(Me2NCH2CH2)C2B10H11]YCl(MeCN)3·MeCN (3·MeCN). Treatment of 2 with 1 equiv of Cp‘ ‘Li in THF gave [η 1:η 6-(Me2NCH2CH2)C2B10H11]YCp‘ ‘(μ-Cl)Li(THF)2 (4). Interaction of 2 with AgBPh4 or potassium phthalimide gave neutral carborane 1 and other unidentified species. Amine elimination reaction is an effective method for the production of half-sandwich lanthanacarborans. Treatment of 7-Me2NHCH2CH2-7,8-C2B9H11 (5) with Ln[N(SiHMe2)2]3(THF)2 or ClY[N(SiHMe2)2]2(THF) x afforded [η 1:η 5-(Me2NCH2CH2)C2B9H10]Ln[N(SiHMe2)2](THF)2 (Ln = Sm (6), Er (7)) or [η 1:η 5-(Me2NCH2CH2)C2B9H10]YCl(THF)2 (8), respectively. Complex 8 was also prepared from an equimolar reaction of K2[Me2NCH2CH2C2B9H10] with YCl3 in THF. [η 1:η 1:η 5-(Me2NCH2CH2)(MeOCH2CH2)C2B9H9]Y(μ-Cl)2K(THF)2 (10) was prepared in a similar manner from the reaction of K2[(Me2NCH2CH2)(MeOCH2CH2)C2B9H9] with YCl3. Complex 10 underwent partial hydrolysis to produce [YCl2(THF)5][nido-(Me2NCH2CH2)(MeOCH2CH2)C2B9H10]·THF (11·THF). On the other hand, treatment of K2[(Me2NCH2CH2)(MeOCH2CH2)C2B9H9] with 1 equiv of Cp‘ ‘2LnI in THF afforded mixed-sandwich lanthanacarboranes [η 1:η 1:η 5-(Me2NCH2CH2)(MeOCH2CH2)C2B9H9]LnCp‘ ‘ (Ln = Y (12), Er (13)). Complex 12 was also prepared from an equimolar reaction of 10 with Cp‘ ‘Li in THF. All complexes were fully characterized by various spectroscopic techniques and elemental analyses. Complexes 3, 4, 6−8, and 11−13 were further confirmed by single-crystal X-ray analyses.

show abstract

Section: Resultssupporting

confidence: 58%

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C₂B₉ and C₂B₁₀ Systems

2005

View full text Add to dashboard Cite

show abstract

“…All the (NN fc )MBn(THF) and (NN fc )MI(THF) z complexes were characterized by X-ray crystallography. Structurally characterized organometallic complexes of holmium, − erbium, − and gadolinium ,− are rare. (NN fc )NdBn(THF) (Figure SX5), (NN fc )GdBn(THF) (Figure SX6), (NN fc )HoBn(THF) (Figure ), and (TBS)ErBn(THF) (Figure SX8) are isostructural with (NN fc )YBn(THF) .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

et al. 2013

View full text Add to dashboard Cite

The organometallic chemistry of paramagnetic lanthanides (Ln, from Ce to Yb) is far less developed compared to that of their diamagnetic counterparts (Sc, Y, La, and Lu). Lack of available starting materials and characterization methods are the major obstacles. Herein we report the synthesis and characterization of trisbenzyl complexes of neodymium, gadolinium, holmium, and erbium. In addition, we introduce a direct procedure for the synthesis of lanthanide benzyl and iodide complexes supported by a ferrocene diamide ligand starting from the corresponding oxides. All newly synthesized compounds were characterized by X-ray crystallography, 1 H NMR spectroscopy (except for gadolinium compounds, which were NMR silent), and elemental analysis.

show abstract

“…With this in mind, we initiated an investigation of a simple, direct route to the synthesis of such complexes. The initial results of this investigation were described in a preliminary communication . Herein, we report a more extensive application of the method, along with the structural characterizations of the products.…”

Section: Introductionmentioning

confidence: 96%

“…The initial results of this investigation were described in a preliminary communication. 10 Herein, we report a more extensive application of the method, along with the structural characterizations of the products. In addition, the limitations of the method were investigated using CpLnCl 2 , Cp 2 -LnCl, and (C 8 H 8 )LnCl as well as LnX 3 (X ) Cl or Br) as lanthanide sources.…”

Section: Introductionmentioning

confidence: 99%

Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 32. Synthetic and Structural Investigations on Half-Sandwich Lanthanacarboranes: Important Synthons in Metallacarborane Chemistry

et al. 2006

Self Cite

View full text Add to dashboard Cite

The reactivities of the monosodium-complexed carborane precursors nido-1-Na(C4H8O)-2-(R)-3-(SiMe3)-2,3-C2B4H5 (R = SiMe3 (1) or Me (2)) with a number of lanthanide halides were investigated. The reaction of LnCl3 (or LnBr3) with 1 in a 1:2 molar ratio in dry THF at 60 °C produced the dimerized half-sandwich lanthanacarborane complexes [2,3-(SiMe3)2-1-X-1-(THF) m -1-Ln(η5-2,3-C2B4H4)]2·n(THF) (3, Ln = Y, X = Cl, m = 2, n = 1; 4, Ln = La, X = Br; m = 1, n = 0; 5, Ln = Ce, X = Br; m = 1, n = 0; 6, Ln = Pr, X = Br; m = 2, n = 1; 7, Ln = Nd; X = Cl, m = 2, n = 1; 8, Ln = Sm; X = Br, m = 2, n = 0; 9, Ln = Gd; X = Cl, m = 2, n = 1; 10, Ln = Tb, X = Cl, m = 2, n = 1; 11, Ln = Dy, X = Cl, m = 2, n = 1; 12, Ln = Ho, X = Cl, m = 2, n = 1; 13, Ln = Er, X = Cl, m = 2, n = 1; 14, Ln = Tm, X = Cl, m = 2, n = 1; 15, Ln = Yb, X = Cl, m = 2, n = 1; 16, Ln = Lu X = Cl, m = 2, n = 1) as crystalline solids in 70−92% isolated yields. In a similar manner, the reactions of 2 with LnCl3 at 65 °C gave the corresponding complexes [2-Me-3-(SiMe3)-1-Cl-1-(THF)2-1-Ln(η5-2,3-C2B4H4)]2 (17, Ln = Nd; 18, Ln = Dy; 19, Ln = Ho; 20, Ln = Er; 21, Ln = Yb) as crystalline solids in 72−80% yield. In both series of the reactions, 1 equiv of the particular neutral carborane was also produced. The substitution of the chloride ions in complexes 17 and 20 by 2 gave the half-sandwich lanthanacarborane clusters {2-Me-3-(SiMe3)-1-[4,5-(μ-H)-nido-2-Me-3-(SiMe3)-2,3-C2B4H5]-1-Ln(η5-2,3-C2B4H4)}2·n(THF) (22, Ln = Nd, n = 2; 24, Ln = Er, n = 1) as crystalline solids in 82−87% yield. The reaction of 19 and 2 produced the trimer {2-Me-3-(SiMe3)-1-[4,5-(μ-H)-nido-2-Me-3-(SiMe3)-2,3-C2B4H5]-1-Ho(η5-2,3-C2B4H4)}3·8(THF) (23) in 57% yield. Complexes 22, 23, and 24 could directly be obtained in good yield (56−67%) from the reaction of 2 with the corresponding LnCl3 at 65 °C in molar ratios of 3:1 in dry THF. Similarly, the mixed coordinated complex {2,3-(SiMe3)2-1-[4,5-(μ-H)-(nido-2-Me-3-(SiMe3)-2,3-C2B4H5)]-1-Gd(η5-2,3-C2B4H4)}2·3(THF) (25) was obtained by reacting compound 9 with 2. To investigate the importance of the halide in these reactions, (η5-Cp)LnCl2 (Ln = Tb, Dy, Er) with 1 in a 1:2 molar ratio produced lanthanacarborane complexes [1-(η5-C5H5)-2,3-(SiMe3)2-1-Ln(η5-2,3-C2B4H4)]2·n(THF) (26, Ln = Tb, n = 2; 27, Ln = Dy, n = 2; 28, Ln = Er, n = 3) as crystalline solids in 77−82% isolated yields. On the other hand, the reactions of (η5-Cp)2ErCl and (η8-C8H8)GdCl with 1 in 1:1 molar ratios did not produce the half-sandwich lanthanacarboranes, but rather gave the exo-polyhedral products {exo-(η5-C5H5)2Er[4,5-(μ-H)-2,3-(SiMe3)2-2,3-C2B4H4]}·(THF) (29) and {exo-(η8-C8H8)Gd[4,5-(μ-H)-2,3-(SiMe3)2-2,3-C2B4H4]·2(THF) (30) as crystalline solids in 76% and 73% isolated yield, respectively. All compounds were characterized by IR spectroscopy and elemental analysis, whereas compounds 3, 7−9, 10−16, 18−22, 29, and 30 were characterized by single-crystal X-ray diffraction studies. The diamagnetic compounds 3, 4, and 16 were additionally characterized by 1H, 13C, and 11B NMR s...

show abstract

Half-sandwich halolanthanacarboranes of the “carbons adjacent” C2B4-carborane ligand systems: important synthons for new polyhedral cage constructs

Cited by 9 publications

References 19 publications

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C₂B₉ and C₂B₁₀ Systems

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C₂B₉ and C₂B₁₀ Systems

Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 32. Synthetic and Structural Investigations on Half-Sandwich Lanthanacarboranes: Important Synthons in Metallacarborane Chemistry

Contact Info

Product

Resources

About

Half-sandwich halolanthanacarboranes of the “carbons adjacent” C2B4-carborane ligand systems: important synthons for new polyhedral cage constructs

Cited by 9 publications

References 19 publications

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C2B9 and C2B10 Systems

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C2B9 and C2B10 Systems

Synthesis and Characterization of Paramagnetic Lanthanide Benzyl Complexes

Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 32. Synthetic and Structural Investigations on Half-Sandwich Lanthanacarboranes: Important Synthons in Metallacarborane Chemistry

Contact Info

Product

Resources

About

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C₂B₉ and C₂B₁₀ Systems

Synthesis, Structural Characterization, and Reactivity of Rare Earth Complexes Incorporating Lewis Base Appended nido-Carborane Anions of the C₂B₉ and C₂B₁₀ Systems