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

Litwin Jacob; Edyta Rzeszotarska; Anna Pietrzak; Victor G. Young; Piotr Kaszyński

doi:10.1002/ejic.202000456

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

Litwin Jacob, Edyta Rzeszotarska, Anna Pietrzak, Victor G. Young, Piotr Kaszyński

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	3083-3093
Number of pages	11
Journal	European Journal of Inorganic Chemistry
Volume	2020
Issue number	32
DOIs	https://doi.org/10.1002/ejic.202000456
State	Published - Aug 31 2020

Bibliographical note

Funding Information:
This work was supported by the Foundation for Polish (TEAM/2016‐3/24) and European Space Agency (NPI 542). We thank Dr. Bryan Ringstrand for supplying crystals of 1f for XRD analysis.

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

Boron
Cluster compounds
Density functional calculations
Structure elucidation
Synthesis design

Publisher link

10.1002/ejic.202000456

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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. / Jacob, Litwin; Rzeszotarska, Edyta; Pietrzak, Anna et al.
In: European Journal of Inorganic Chemistry, Vol. 2020, No. 32, 31.08.2020, p. 3083-3093.

Research output: Contribution to journal › Article › peer-review

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

abstract = "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.",

keywords = "Boron, Cluster compounds, Density functional calculations, Structure elucidation, Synthesis design",

author = "Litwin Jacob and Edyta Rzeszotarska and Anna Pietrzak and Young, {Victor G.} and Piotr Kaszy{\'n}ski",

note = "Funding Information: This work was supported by the Foundation for Polish (TEAM/2016‐3/24) and European Space Agency (NPI 542). We thank Dr. Bryan Ringstrand for supplying crystals of 1f for XRD analysis. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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T1 - Synthesis, Structural Analysis, and Functional Group Interconversion in the [closo-B10H8-1,10-X2]2– (X = CN, [OCRNMe2]+, OCOR, and [OH2]+) Derivatives

AU - Jacob, Litwin

AU - Rzeszotarska, Edyta

AU - Pietrzak, Anna

AU - Young, Victor G.

AU - Kaszyński, Piotr

N1 - Funding Information: This work was supported by the Foundation for Polish (TEAM/2016‐3/24) and European Space Agency (NPI 542). We thank Dr. Bryan Ringstrand for supplying crystals of 1f for XRD analysis. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/8/31

Y1 - 2020/8/31

N2 - 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.

AB - 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.

KW - Boron

KW - Cluster compounds

KW - Density functional calculations

KW - Structure elucidation

KW - Synthesis design

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DO - 10.1002/ejic.202000456

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SN - 1434-1948

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EP - 3093

JO - Chemische Berichte

JF - Chemische Berichte

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