New synthetic routes to B-halogenated derivatives of cobalt dicarbollide

Hurlburt, Paul K.; Miller, Rebecca L.; Abney, Kent D.; Foreman, Trudi; Butcher, Raymond J.; Kinkhead, Scott A.

doi:10.1021/ic00125a021

Cited by 63 publications

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“…At the same time, the other bond lengths in 7 are comparable with the analogous bond lengths in 6 ( Table 4). The Cl(1)-B (6) and Cl(2)-B(11) distances in 7 are 1.817(2) Å and 1.807(2) Å respectively, which is similar to the values in [14][15][16][17][18]. In the crystal structure, the molecules form rows along the c axis; the directions of the Me 2 S substituents alternate in these rows.…”

Section: Resultssupporting

confidence: 61%

Structure of 6,11-dichloro-9-dimethylthio-7,8-dicarba-nido-undecaborane [6,11-Cl2-9-SMe2-7,8-C2B9H9]

et al. 2013

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Section: Resultssupporting

confidence: 61%

Structure of 6,11-dichloro-9-dimethylthio-7,8-dicarba-nido-undecaborane [6,11-Cl2-9-SMe2-7,8-C2B9H9]

et al. 2013

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“…[24] In this regard, regiospecific syntheses of 8-I and 8,8'-I 2 [25] have been described, but no 8-alkyl/aryl derivatives have been reported. As mentioned by Bregadze in 1992, [26] halogeno derivatives appear to be inert towards substitution reactions, although Hawthorne and co-workers have recently shown that starting from [3,3'-Co(8,9,12-I 3 -1,2-C 2 B 9 H 8 ) 2 ]…”

Section: Introductionmentioning

confidence: 99%

Relevance of the Electronegativity of Boron in η⁵‐Coordinating Ligands: Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3′‐Co(1,2‐C₂B₉H₁₁)₂]⁻ Clusters

Rojo

Teixidor

Viñas

et al. 2003

Chemistry A European J

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Regioselective monoalkylation and monoarylation in cobaltabisdicarbollide clusters has been achieved starting from Cs[8-I-3,3'-Co(1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))] by cross-coupling reactions between a B-I fragment and an appropriate Grignard reagent in the presence of a Pd catalyst and CuI. A considerable number of monoalkylated and monoarylated derivatives have been synthesized, which allowed study of the influence of boron in metallocene-type ligands and the effect of alkyl and aryl substituents on boron in boron anionic clusters. Experimental data from UV/Vis spectroscopy, E(1/2) measurements, and X-ray diffraction analysis, and supported by EHMO and ab initio analyses, indicate that the participation of metal d orbitals in the HOMO is less than that in typical metallocene complexes. This can be explained in terms of the lower electronegativity of boron compared to carbon. Related to this is the -I character of alkyl groups when bonded to boron in boron anionic clusters, contrary to the common belief that alkyl groups are generally electron-releasing moieties.

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“…[33] On the other hand, pure 2 ] has been reported to be synthesised by reaction of N-chlorosuccinimide with Cs [1] in THF. [34] To easily correlate the number of Cl substituents on platform 1 À and the additive potential shift described in this work, we have named the halogenated species…”

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confidence: 99%

Additive Tuning of Redox Potential in Metallacarboranes by Sequential Halogen Substitution

González-Cardoso¹,

Stoica²,

Farràs³

et al. 2010

Chemistry A European J

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The first artificially made set of electron acceptors is presented that are derived from a unique platform Cs[3,3'-Co(C(2)B(9)H(11))(2)], for which the redox potential of each differs from its predecessor by a fixed amount. The sequence of electron acceptors is made by substituting one, two, or more hydrogen atoms by chlorine atoms, yielding Cs[3,3'-Co(C(2)B(9)H(11-y)Cl(y))(C(2)B(9)H(11-z)Cl(z))]. The higher the number of chlorine substituents, the more prone the platform is to be reduced. The effect is completely additive, so if a single substitution implies a reduction of 0.1 V of the redox potential of the parent complex, then ten substitutions imply a reduction of 1 V.

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New synthetic routes to B-halogenated derivatives of cobalt dicarbollide

Cited by 63 publications

References 0 publications

Structure of 6,11-dichloro-9-dimethylthio-7,8-dicarba-nido-undecaborane [6,11-Cl2-9-SMe2-7,8-C2B9H9]

Structure of 6,11-dichloro-9-dimethylthio-7,8-dicarba-nido-undecaborane [6,11-Cl2-9-SMe2-7,8-C2B9H9]

Relevance of the Electronegativity of Boron in η⁵‐Coordinating Ligands: Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3′‐Co(1,2‐C₂B₉H₁₁)₂]⁻ Clusters

Additive Tuning of Redox Potential in Metallacarboranes by Sequential Halogen Substitution

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New synthetic routes to B-halogenated derivatives of cobalt dicarbollide

Cited by 63 publications

References 0 publications

Structure of 6,11-dichloro-9-dimethylthio-7,8-dicarba-nido-undecaborane [6,11-Cl2-9-SMe2-7,8-C2B9H9]

Structure of 6,11-dichloro-9-dimethylthio-7,8-dicarba-nido-undecaborane [6,11-Cl2-9-SMe2-7,8-C2B9H9]

Relevance of the Electronegativity of Boron in η5‐Coordinating Ligands: Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3′‐Co(1,2‐C2B9H11)2]− Clusters

Additive Tuning of Redox Potential in Metallacarboranes by Sequential Halogen Substitution

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Relevance of the Electronegativity of Boron in η⁵‐Coordinating Ligands: Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide [3,3′‐Co(1,2‐C₂B₉H₁₁)₂]⁻ Clusters