Convenient Synthesis of [closo-B10H9-1-I]2– and [closo-B10H8-1,10-I2]2– Anions

Rzeszotarska, Edyta; Novozhilova, Irina V.; Kaszyński, Piotr

doi:10.1021/acs.inorgchem.7b02477

Cited by 28 publications

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References 53 publications

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“…In both cases, the sulfonium group has a stronger effect on the cage geometry than that of the pyridinium substituent. Similar substituent effects on the cluster dimensions have been observed previously, including derivatives of anions [ closo ‐1‐CB 9 H 10 ] −[34] and A …”

Section: Resultssupporting

confidence: 79%

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B₁₂H₁₂]²⁻ Anion

Ali

Lasseter

Żurawiński

et al. 2019

Chemistry A European J

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Two series of 1,12‐bis‐zwitterionic derivatives of the [closo‐B12H12]2− anion (B), containing either two 4‐alkoxypyridinium groups (1B[n]‐p) or one 4‐alkoxypyridinium and one 4‐pentylthianium groups (2B[n]‐p), were prepared and their structural (XRD, DFT), thermal, and photophysical properties were compared with those of the analogous derivatives of the [closo‐B10H10]2− anion (1A[n]‐p and 2A[n]‐p). Some 1,7‐derivatives of B were isolated and investigated. Both series 1[n] and 2[n] exhibit nematic and crystalline polymorphism; the 12‐vertex derivatives (B) have higher transition temperatures than those of the 10‐vertex analogues (A). All compounds fluoresce with quantum yields higher for 1B (ΦF=0.37 for 1B[7]‐p and ΦF=0.27 for 2B[7]‐p) than those for the 10‐vertex analogues (ΦF=0.04 for 2A[5]‐p). DFT calculations demonstrate an order of magnitude lower first hyperpolarizability, β(−ω,ω,0), for 2B[7]‐p than that for the 10‐vertex analogue 2A[7]‐p (1.7×10−30 vs. 18.9×10−30 esu at ω=0).

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Section: Resultssupporting

confidence: 79%

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B₁₂H₁₂]²⁻ Anion

Ali

Lasseter

Żurawiński

et al. 2019

Chemistry A European J

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“…Data in Table show that the { closo ‐B 10 } cage dimensions in 1f and 1h – 1k (Figure ) are typical for { closo ‐B 10 } derivatives as exemplified with the parent A and derivatives 1a , 1g , and also [ closo ‐1‐B 10 H 8 ‐1,10‐(NC 5 H 5 ) 2 ] ( 1o ) and [ closo ‐1‐B 10 H 8 ‐1,10‐(SMe 2 ) 2 ] ( 1p ) . Analysis of the data indicates that the cage geometry responds to the nature of the apical substituent.…”

Section: Resultsmentioning

confidence: 94%

“…The issue of an alternative synthesis of diacid 1e avoiding CO under high pressure still remains open. One potentially attractive approach to 1e is Pd‐catalyzed carbonylation of the readily available diiodide 1g , using CO surrogates.…”

Section: Discussionmentioning

confidence: 99%

“…The only previously reported [ closo ‐B 10 H 9 ‐1‐OH] 2– was obtained in 82 % yield by decomposition of monodinitrogen derivative [ closo ‐B 10 H 9 ‐1‐N 2 ] – in aqueous NaF, while the equatorial isomer [ closo ‐B 10 H 9 ‐2‐OH] 2– was easily prepared by alkaline hydrolysis of the formate or acetate ester . The readily available [ closo ‐B 10 H 9 ‐1‐IPh] – offers a potentially alternative route to the 1‐hydroxy derivative following the sequence described for 1h‐2H .…”

Section: Discussionmentioning

confidence: 99%

“…Recently, we discovered a highly selective and high yield formation of the bis‐phenyliodonium derivative [ closo ‐B 10 H 8 ‐1,10‐(IPh) 2 ] ( 1f , Figure ), which undergoes nucleophilic substitution reactions through the 10‐I‐3 intermediate,[5a], , or efficient dephenylation through the 9‐I‐2 intermediate and formation of [ closo ‐B 10 H 8 ‐1,10‐I 2 ] 2– ( 1g ) . This demonstrates a great potential for 1f as a more efficient and convenient intermediate than 1a to 1,10‐difunctionalized derivatives of A .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo‐B₁₀H₈‐1,10‐X₂]²^– (X = CN, [OCRNMe₂]⁺, OCOR, and [OH₂]⁺) Derivatives

et al. 2020

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Derivatives [closo‐B10H8‐1,10‐(CN)2]2– and [closo‐B10H8‐1,10‐(OCHNMe2)2], efficiently obtained from [closo‐B10H8‐1,10‐(IPh)2] by nucleophilic substitution with CN– and DMF, were envisioned as precursors to diacid [closo‐B10H8‐1,10‐(COOH)2]2– and to dihydroxy derivative [closo‐B10H8‐1,10‐(OH)2]2–, respectively. Attempts at hydrolysis or reduction of the dinitrile gave no reaction or complex mixtures of products. In contrast, the DMF adduct was cleanly hydrolyzed to diformate [closo‐B10H8‐1,10‐(OCHO)2]2– and subsequently to protonated dihydroxy [closo‐B10H8‐1,10‐(OH2)2]. The latter was O‐acylated with PhCOCl. Crystal and molecular structures of five derivatives were established by single crystal XRD methods and compared to those for other [closo‐B10H8‐1,10‐X2]2– derivatives. Trends in molecular geometry in the series and also reactivity of the dinitrile and intermediates were corroborated and correlated with DFT results (B3LYP/TZVP) by analysis of bonding, charge distribution and vibrational frequencies.

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NMRof Hypervalent Iodine Compounds

Shafir

2018

Patai's Chemistry of Functional Groups

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Nuclear magnetic resonance (NMR) spectroscopy has played a key role in the rise of modern high‐valent halogen chemistry, especially for gaining solution‐state information on the corresponding organic derivatives. This chapter is focused on those aspects of NMR that have somehow proven specific to this family of compounds, including instances of abnormal chemical shifts, the highly electron‐withdrawing nature of the iodane group, and the presence of highly ionic hypervalent bond. In addition, the essay includes aspects that have had a particular impact on the development of this area of chemistry. The chapter is divided into six sections, with Section I introducing some of the general aspects of the NMR spectroscopy of high‐valent organoiodine species, including the normal halogen dependence (NHD) explanation for certain chemical shift abnormalities, the general iodine oxidation state influence on 1 H and 13 C chemical shifts, and certain challenges of solution‐state measurements for this class of compounds. Section II presents a discussion on the difficulty of directly measuring the halogen chemical shifts due to the nucleus' high quadrupole moments, especially for 127 I. Sections III and IV contain a discussion of some of the most relevant 13 C and 19 F NMR studies, including the key contributions of these two techniques to the understanding of the physical organic chemistry aspects of high‐valent halogen derivatives. Section V is dedicated to the NMR characterization via the less‐common nuclei, specifically 11 B, 31 P, 29 Si, and 17 O NMR, and includes a discussion of the role played by 17 O NMR in establishing the dynamic nature of certain key high‐valent carboxylates. Finally, Section VI presents a series of selected studies in which NMR is used to shed light on the mechanism of processes involving high‐valent iodine reagents.

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Convenient Synthesis of [closo-B₁₀H₉-1-I]^2– and [closo-B₁₀H₈-1,10-I₂]^2– Anions

Cited by 28 publications

References 53 publications

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B₁₂H₁₂]²⁻ Anion

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B₁₂H₁₂]²⁻ Anion

Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo‐B₁₀H₈‐1,10‐X₂]²^– (X = CN, [OCRNMe₂]⁺, OCOR, and [OH₂]⁺) Derivatives

NMRof Hypervalent Iodine Compounds

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Convenient Synthesis of [closo-B10H9-1-I]2– and [closo-B10H8-1,10-I2]2– Anions

Cited by 28 publications

References 53 publications

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B12H12]2− Anion

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B12H12]2− Anion

Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo‐B10H8‐1,10‐X2]2– (X = CN, [OCRNMe2]+, OCOR, and [OH2]+) Derivatives

NMRof Hypervalent Iodine Compounds

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Convenient Synthesis of [closo-B₁₀H₉-1-I]^2– and [closo-B₁₀H₈-1,10-I₂]^2– Anions

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B₁₂H₁₂]²⁻ Anion

Thermal and Photophysical Properties of Highly Quadrupolar Liquid‐Crystalline Derivatives of the [closo‐B₁₂H₁₂]²⁻ Anion

Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo‐B₁₀H₈‐1,10‐X₂]²^– (X = CN, [OCRNMe₂]⁺, OCOR, and [OH₂]⁺) Derivatives