Toward the synthesis of high boron content polyanionic multicluster macromolecules

Pau Farràs; Ana Maria Cioran; Václav Šícha; Francesc Teixidor; Bohumil Štíbr; Bohumír Grüner; Clara Viñas

doi:10.13025/15100

Toward the synthesis of high boron content polyanionic multicluster macromolecules

Pau Farràs
, Ana Maria Cioran
, Václav Šícha
, Francesc Teixidor
, Bohumil Štíbr
, Bohumír Grüner
, Clara Viñas

Autonomous University of Barcelona (UAB)
Institute of Inorganic Chemistry of the Czech Academy of Sciences

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

22 Citations (Scopus)

Abstract

Reported are further consequences of the dioxane ring opening in [3,3′-Co(8-(CH₂CH₂O)₂-1,2-C ₂B₉H₁₀)(1′,2′-C₂B ₉H₁₁)], [1], with 12-vertex carborane mono- and dianions. The removal of one BH vertex from the 1,2-closo-C₂B₉H ₁₂ part of the double-cluster monoanions of type [1″-X- 2″-R-closo-1″,2″-C₂B₁₀H ₁₁]_-, [2]^- (where X = [3,3′-Co(8-(CH ₂CH₂O)₂-1,2C₂B₉H ₁₀)(1′,2′-C₂B₉H₁₁)] and R = H, [2]^-; CH_3, [8]_- and C₆H ₅, [9^-]), via heating with ethanolic KOH or CsF led to the isolation of a series of orange dianions having the general formula [7″-X-8″-R-7″,8″-nido -C₂B₉H ₁₁]^2- (R = H, [11]² ; CH_3, [12] ^2-; and-C₆H_5,[13]_2-). The same procedure applied to the dianionic triple-cluster compound [1″,2″- X₂-1″,2″-closoC₂B₁₀H ₁₀]^2-, [5]^2- , yielded the trianionic species [7″,8′-X₂7″,8″-nido -C₂B ₉H₁₀]^3-, [14]^3-. Boron degradation of the related 1,7-carborane anion [1 ″-X-1 ″,7″-Closo-C ₂B₁₀H₁₁]^-, [3]^-, was achieved upon heating with CsF in ethylene glycol to generate the [7″-X-7″,9″-nido-C₂B₉H ₁₁]^2-, [15]^2- , dianion. However, the degradation of the corresponding [1″,7″-X₂1″, 7″-closo-C₂B₁₀H₁₀]^2-, [6] ^2-, dianion under the same conditions led only to the cleavage of the ether chain with no possible isolation of the expected [7″,9″- X₂-7″,9″-nido-C₂B₉H ₁₀]^3- trianion. The study has been complemented by experimental procedures leading to the still not fully reported starting monoanionic compounds [2]^-, [3]^-, [8]^- and [9]^- and to the starting dianions [5]^2- and [6] ^2-. The anions containing the eleven-vertex moiety can be isolated as either Cs⁺ or [N(CH₃)₄]⁺ salts and can be converted into other salts via metathesis with suitable countercations. The structures of all compounds isolated in this study have been suggested on the basis of NMR and mass spectrometry methods. The disarticulation of complex ¹¹B NMR spectra has been successfully achieved in this work and has been proven to be a powerful tool for the characterization of multicluster boron-containing molecules.

Original language	English
Pages (from-to)	8210-8219
Number of pages	10
Journal	Inorganic Chemistry
Volume	48
Issue number	17
DOIs	https://doi.org/10.13025/15100 https://doi.org/10.1021/ic9006907
Publication status	Published - 7 Sept 2009
Externally published	Yes

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10.13025/15100Licence: CC BY-NC-ND
10.1021/ic9006907

Inorg Chem 2009 TowardsdocxAccepted author manuscript, 961 KBLicence: CC BY-NC-ND

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@article{dc3faaa533b947f6aa96647fc66a647d,

title = "Toward the synthesis of high boron content polyanionic multicluster macromolecules",

abstract = "Reported are further consequences of the dioxane ring opening in [3,3′-Co(8-(CH2CH2O)2-1,2-C 2B9H10)(1′,2′-C2B 9H11)], [1], with 12-vertex carborane mono- and dianions. The removal of one BH vertex from the 1,2-closo-C2B9H 12 part of the double-cluster monoanions of type [1″-X- 2″-R-closo-1″,2″-C2B10H 11]-, [2]- (where X = [3,3′-Co(8-(CH 2CH2O)2-1,2C2B9H 10)(1′,2′-C2B9H11)] and R = H, [2]-; CH3, [8]- and C6H 5, [9-]), via heating with ethanolic KOH or CsF led to the isolation of a series of orange dianions having the general formula [7″-X-8″-R-7″,8″-nido -C2B9H 11]2- (R = H, [11]2 ; CH3, [12] 2-; and-C6H5,[13]2-). The same procedure applied to the dianionic triple-cluster compound [1″,2″- X2-1″,2″-closoC2B10H 10]2-, [5]2- , yielded the trianionic species [7″,8′-X27″,8″-nido -C2B 9H10]3-, [14]3-. Boron degradation of the related 1,7-carborane anion [1 ″-X-1 ″,7″-Closo-C 2B10H11]-, [3]-, was achieved upon heating with CsF in ethylene glycol to generate the [7″-X-7″,9″-nido-C2B9H 11]2-, [15]2- , dianion. However, the degradation of the corresponding [1″,7″-X21″, 7″-closo-C2B10H10]2-, [6] 2-, dianion under the same conditions led only to the cleavage of the ether chain with no possible isolation of the expected [7″,9″- X2-7″,9″-nido-C2B9H 10]3- trianion. The study has been complemented by experimental procedures leading to the still not fully reported starting monoanionic compounds [2]-, [3]-, [8]- and [9]- and to the starting dianions [5]2- and [6] 2-. The anions containing the eleven-vertex moiety can be isolated as either Cs+ or [N(CH3)4]+ salts and can be converted into other salts via metathesis with suitable countercations. The structures of all compounds isolated in this study have been suggested on the basis of NMR and mass spectrometry methods. The disarticulation of complex 11B NMR spectra has been successfully achieved in this work and has been proven to be a powerful tool for the characterization of multicluster boron-containing molecules.",

author = "Pau Farr{\`a}s and Cioran, \{Ana Maria\} and V{\'a}clav {\v S}{\'i}cha and Francesc Teixidor and Bohumil {\v S}t{\'i}br and Bohum{\'i}r Gr{\"u}ner and Clara Vi{\~n}as",

year = "2009",

month = sep,

day = "7",

doi = "10.13025/15100",

language = "English",

volume = "48",

pages = "8210--8219",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - Toward the synthesis of high boron content polyanionic multicluster macromolecules

AU - Farràs, Pau

AU - Cioran, Ana Maria

AU - Šícha, Václav

AU - Teixidor, Francesc

AU - Štíbr, Bohumil

AU - Grüner, Bohumír

AU - Viñas, Clara

PY - 2009/9/7

Y1 - 2009/9/7

N2 - Reported are further consequences of the dioxane ring opening in [3,3′-Co(8-(CH2CH2O)2-1,2-C 2B9H10)(1′,2′-C2B 9H11)], [1], with 12-vertex carborane mono- and dianions. The removal of one BH vertex from the 1,2-closo-C2B9H 12 part of the double-cluster monoanions of type [1″-X- 2″-R-closo-1″,2″-C2B10H 11]-, [2]- (where X = [3,3′-Co(8-(CH 2CH2O)2-1,2C2B9H 10)(1′,2′-C2B9H11)] and R = H, [2]-; CH3, [8]- and C6H 5, [9-]), via heating with ethanolic KOH or CsF led to the isolation of a series of orange dianions having the general formula [7″-X-8″-R-7″,8″-nido -C2B9H 11]2- (R = H, [11]2 ; CH3, [12] 2-; and-C6H5,[13]2-). The same procedure applied to the dianionic triple-cluster compound [1″,2″- X2-1″,2″-closoC2B10H 10]2-, [5]2- , yielded the trianionic species [7″,8′-X27″,8″-nido -C2B 9H10]3-, [14]3-. Boron degradation of the related 1,7-carborane anion [1 ″-X-1 ″,7″-Closo-C 2B10H11]-, [3]-, was achieved upon heating with CsF in ethylene glycol to generate the [7″-X-7″,9″-nido-C2B9H 11]2-, [15]2- , dianion. However, the degradation of the corresponding [1″,7″-X21″, 7″-closo-C2B10H10]2-, [6] 2-, dianion under the same conditions led only to the cleavage of the ether chain with no possible isolation of the expected [7″,9″- X2-7″,9″-nido-C2B9H 10]3- trianion. The study has been complemented by experimental procedures leading to the still not fully reported starting monoanionic compounds [2]-, [3]-, [8]- and [9]- and to the starting dianions [5]2- and [6] 2-. The anions containing the eleven-vertex moiety can be isolated as either Cs+ or [N(CH3)4]+ salts and can be converted into other salts via metathesis with suitable countercations. The structures of all compounds isolated in this study have been suggested on the basis of NMR and mass spectrometry methods. The disarticulation of complex 11B NMR spectra has been successfully achieved in this work and has been proven to be a powerful tool for the characterization of multicluster boron-containing molecules.

AB - Reported are further consequences of the dioxane ring opening in [3,3′-Co(8-(CH2CH2O)2-1,2-C 2B9H10)(1′,2′-C2B 9H11)], [1], with 12-vertex carborane mono- and dianions. The removal of one BH vertex from the 1,2-closo-C2B9H 12 part of the double-cluster monoanions of type [1″-X- 2″-R-closo-1″,2″-C2B10H 11]-, [2]- (where X = [3,3′-Co(8-(CH 2CH2O)2-1,2C2B9H 10)(1′,2′-C2B9H11)] and R = H, [2]-; CH3, [8]- and C6H 5, [9-]), via heating with ethanolic KOH or CsF led to the isolation of a series of orange dianions having the general formula [7″-X-8″-R-7″,8″-nido -C2B9H 11]2- (R = H, [11]2 ; CH3, [12] 2-; and-C6H5,[13]2-). The same procedure applied to the dianionic triple-cluster compound [1″,2″- X2-1″,2″-closoC2B10H 10]2-, [5]2- , yielded the trianionic species [7″,8′-X27″,8″-nido -C2B 9H10]3-, [14]3-. Boron degradation of the related 1,7-carborane anion [1 ″-X-1 ″,7″-Closo-C 2B10H11]-, [3]-, was achieved upon heating with CsF in ethylene glycol to generate the [7″-X-7″,9″-nido-C2B9H 11]2-, [15]2- , dianion. However, the degradation of the corresponding [1″,7″-X21″, 7″-closo-C2B10H10]2-, [6] 2-, dianion under the same conditions led only to the cleavage of the ether chain with no possible isolation of the expected [7″,9″- X2-7″,9″-nido-C2B9H 10]3- trianion. The study has been complemented by experimental procedures leading to the still not fully reported starting monoanionic compounds [2]-, [3]-, [8]- and [9]- and to the starting dianions [5]2- and [6] 2-. The anions containing the eleven-vertex moiety can be isolated as either Cs+ or [N(CH3)4]+ salts and can be converted into other salts via metathesis with suitable countercations. The structures of all compounds isolated in this study have been suggested on the basis of NMR and mass spectrometry methods. The disarticulation of complex 11B NMR spectra has been successfully achieved in this work and has been proven to be a powerful tool for the characterization of multicluster boron-containing molecules.

UR - http://hdl.handle.net/10379/5966

UR - https://www.scopus.com/pages/publications/69549135857

U2 - 10.13025/15100

DO - 10.13025/15100

M3 - Article

SN - 0020-1669

VL - 48

SP - 8210

EP - 8219

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 17

ER -

Toward the synthesis of high boron content polyanionic multicluster macromolecules

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