How to Make 8,1,2‐closo‐MC2B9 Metallacarboranes

Man, Wing Y.; Zlatogorsky, Sergey; Tricas, Hugo; Ellis, David; Rosair, Georgina M.; Welch, Alan J.

doi:10.1002/ange.201408395

Cited by 6 publications

(1 citation statement)

References 25 publications

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“…Heteroborane cluster chemistry is an active field of research and many interesting studies have been published in recent years. [1][2][3][4][5][6][7][8][9][10] In heteroborane clusters a BH vertex of a borane cluster skeleton is replaced by a main group element or a transition metal. Following the isolobal principle a BH unit can for example be substituted by a Ge atom or an anionic BH − unit by an N atom.…”

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confidence: 99%

Oxidation of germa- and stanna-closo-dodecaborate

et al. 2015

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The oxidation of closo-heteroborates [GeB11H11](2-) and [SnB11H11](2-) is presented. Upon oxidation germa-closo-dodecaborate yields a symmetrical dimer exhibiting a Ge-Ge bond between two clusters. This dimer shows sulphur insertion into the Ge-Ge bond at room temperature. In contrast, oxidation of the homologous tin cluster results in an unsymmetrical dimer bearing an Sn-B bond between two clusters. The Sn-B dimer is also the product of the hydride abstraction reaction. In the presence of the donor ligand 2,2'-bipyridine, the oxidation of closo-cluster [SnB11H11](2-) leads to the Sn(IV)-half sandwich coordination compound [bipy-SnB11H11] which dissolves in DMSO to give the Sn(IV)-adduct [bipy(DMSO)-SnB11H11].

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Section: Introductionmentioning

confidence: 99%

Oxidation of germa- and stanna-closo-dodecaborate

et al. 2015

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Carborane Substituents Promote Direct Electrophilic Insertion over Reduction–Metalation Reactions

et al. 2016

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Tw o-electron reduction of 1,1'-bis(o-carborane) followed by reaction with [Ru(h-mes)Cl 2 ] 2 affords [8-(1'-1',2'-closo-C 2 B 10 H 11 )-4-(h-mes)-4,1,8-closo-RuC 2 B 10 H 11 ]. Subsequent two-electron reduction of this species and treatment with [Ru(h-arene)Cl 2 ] 2 results in the 14-vertex/12-vertex species [1-(h-mes)-9-(1'-1',2'-closo-C 2 B 10 H 11 )-13-(h-arene)-1,13,2,9-closo-Ru 2 C 2 B 10 H 11 ]b yd irect electrophilic insertion, promoted by the carborane substituent in the 13-vertex/12-vertex precursor.W hen arene = mesitylene (mes), the diruthenium species is fluxional in solution at room temperature in aprocess that makes the metal-ligand fragments equivalent. A unique mechanism for this fluxionality is proposed and is shown to be fully consistent with the observed fluxionality or nonfluxionality of as eries of previously reported 14-vertex dicobaltacarboranes. Thechemistryofbis(carboranes),twocarboraneunitsjoinedtogether by ac onventional two-center two-electron bond, is highly topical. In principle,bis(carboranes) have the capacity to undergo similar reactions to single-cage carboranes but with two important differences,s pecifically 1) reactivity at as ingle cage is likely to be significantly influenced by the presence of al arge,e lectron-withdrawing substituent and 2) the reaction could occur at both cages and such reactivity could be either isolated or cooperative.A ni nteresting example of this second point is provided by the following: four-electron reduction of 1,1'-bis(o-carborane), the trivial name for [1-(1'-1',2'-closo-C 2 B 10 H 11 )-1,2-closo-C 2 B 10 H 11 ], followed by metalation with {CoCp + }f ragments (Cp = cyclopenadienyl), and finally Co II !Co III oxidation, leads to the anticipated racemic and meso diastereoisomers of the 13-vertex cobaltacarborane/13-vertex cobaltacarborane species [1-(1'-4'-Cp-4',1',6'-closo-CoC 2 B 10 H 11 )-4-Cp-4,1,6-closoCoC 2 B 10 H 11 ].[1] In marked contrast, four-electron reduction of 1,1'-bis(o-carborane) followed by metalation with {Ru(pcymene) 2+ }f ragments (p-cymene = 1-i Pr-4-Me-C 6 H 4 )a ffords au nique 13-vertex ruthenacarborane/12-vertex carborane species.Inthis molecule,the Ru atom in the expanded cage is bonded to an exopolyhedral {Ru(p-cymene)} unit by aRu-Ru bond bridged by a[ m-s,h 3 :h 3 ,s-C 6 ] 2À "flyover" ligand formed by the room-temperature reductive cleavage of an arene,the origin of this reduction being the pendant carborane dianion.[2]References [1]a nd [2] represent the only reports to date of the reduction and subsequent metalation of bis(carboranes) and, although they describe very different outcomes,in both cases both carborane units were fully reduced (by the addition of two electrons) before metalation. Herein we describe the results of the reduction of only as ingle cage of 1,1'-bis(o-carborane) followed by metalation, and the consequences of repeating this process.W ef ound that unique linked heteroborane species are produced, one subset of which displays unexpected fluxionality that is traced to the formation ...

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14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study

et al. 2016

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Three isomers of [(Cp*Ru) 2 C 2 B 10 H 12 ], the first examples of 14-vertex heteroboranes containing 14-skeletal electron pairs,have been synthesized by the direct electrophilic insertion of a{Cp*Ru + }fragment into the anion [4-Cp*-4,1,6-RuC 2 B 10 H 12 ] À .A ll three compounds have the same unique polyhedral structure having an approximate C s symmetry and featuring af our-atom trapezoidal face.X -ray diffraction studies could confidently identify only one of the two cage Catoms in each structure.The other Catom position has been established by acombination of i) best fitting of computed and experimental 11 Ba nd 1 HNMR chemical shifts,a nd ii)consideration of the lowest computed energy for series of isomers studied by DFT calculations.I na ll three isomers,o ne cage Catom occupies adegree-4 vertex on the short parallel edge of the trapezium.Supportinginformation (containing the experimental, spectroscopic, crystallographic, and computational details of all new compounds reported herein) and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

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How to Make 8,1,2‐closo‐MC₂B₉ Metallacarboranes

Cited by 6 publications

References 25 publications

Oxidation of germa- and stanna-closo-dodecaborate

Oxidation of germa- and stanna-closo-dodecaborate

Carborane Substituents Promote Direct Electrophilic Insertion over Reduction–Metalation Reactions

14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study

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