Definitive crystal structure of 1,1′-bis[1,2-dicarba-<i>closo</i>-dodecaborane(11)]

Man, Wing Y.; Rosair, Georgina M.; Welch, Alan J.

doi:10.1107/s1600536814023897

Cited by 12 publications

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“…), is the simplest bis(carborane) species, comprising two ortho-carborane units connected by a C-C bond. 1 It was first synthesised by insertion of diacetylene into B 10 frameworks 2 but it is also produced from the CuCl 2 -mediated coupling reactions of mono-or di-lithiated salts of ortho-carborane, 3 although yields by this route are somewhat compromised by the additional formation of C-B and B-B linked isomers. CuCl 2 -coupling was also used to make 1,1′-bis(m-carborane) 3,4 and 1,1′-bis( p-carborane), 4,5 the latter an important starting point for the construction of "carborods", rigid-rod oligomers of para-carborane.…”

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Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)

et al. 2015

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Examples of singly-metallated derivatives of 1,1'-bis(o-carborane) have been prepared and spectroscopically and structurally characterised. Metallation of [7-(1'-1',2'-closo-C2B10H11)-7,8-nido-C2B9H10](2-) with a {Ru(p-cymene)}(2+) fragment affords both the unisomerised species [1-(1'-1',2'-closo-C2B10H11)-3-(p-cymene)-3,1,2-closo-RuC2B9H10] (2) and the isomerised [8-(1'-1',2'-closo-C2B10H11)-2-(p-cymene)-2,1,8-closo-RuC2B9H10] (3), and 2 is easily transformed into 3 with mild heating. Metallation with a preformed {CoCp}(2+) fragment also affords a 3,1,2-MC2B9-1',2'-C2B10 product [1-(1'-1',2'-closo-C2B10H11)-3-Cp-3,1,2-closo-CoC2B9H10] (4), but if CoCl2/NaCp is used followed by oxidation the result is the 2,1,8-CoC2B9-1',2'-C2B10 species [8-(1'-1',2'-closo-C2B10H11)-2-Cp-2,1,8-closo-CoC2B9H10] (5). Compound 4 does not convert into 5 in refluxing toluene, but does do so if it is reduced and then reoxidised, perhaps highlighting the importance of the basicity of the metal fragment in the isomerisation of metallacarboranes. A computational study of 1,1'-bis(o-carborane) is in excellent agreement with a recently-determined precise crystallographic study and establishes that the {1',2'-closo-C2B10H11} fragment is electron-withdrawing compared to H.

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“…Tables S2-S5; computational models. CCDC 1042151-1042155 (salt [BTMA] [1] and compounds 2-5, respectively). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt00081e cages, in a similar manner to the protonation and work-up of [7,9-nido-C 2 B 10 H 12 ] 2− affording [μ 9,10 -CH 2 -7-nido-CB 10 H 11 ] − .…”

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Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)

et al. 2015

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“…175.14(5)°in 1,1′-bis(o-carborane) itself. 1 An analogous compound, [μ-2,2′-PEt-{1-(1′-1′,2′-closo-C 2 B 10 H 10 )-1,2-closo-C 2 B 10 H 10 }] (1), was similarly prepared. The 11 B{ 1 H} NMR spectrum of 1 reveals a 2 : 2 : 6 : 2 : 2 : 6 pattern (high frequency to low frequency) between δ ca.…”

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confidence: 99%

“…Currently, one of the most active areas of carborane chemistry concerns the compound [1-(1′-1′,2′-closo-C 2 B 10 H 11 )-1,2-closo-C 2 B 10 H 11 ], two ortho-carborane units connected by a C-C bond 1 and commonly referred to as 1,1′-bis(o-carborane) ( Fig. 1).…”

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confidence: 99%

Large, weakly basic bis(carboranyl)phosphines: an experimental and computational study

et al. 2017

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The bis(carboranyl)phosphines [μ-2,2'-PPh-{1-(1'-1',2'-closo-CBH)-1,2-closo-CBH}] (I) and [μ-2,2'-PEt-{1-(1'-1',2'-closo-CBH)-1,2-closo-CBH}] (1) have been prepared and spectroscopically and structurally characterised. Crystallographic and DFT computational studies of 1 suggest that the orientation of the ethyl group, relative to the bis(carborane), is the result of intramolecular dihydrogen bonding. This orientation is such that the magnitudes of the J coupling constants are approximately equal but of opposite sign, and fast exchange between the methylene protons in solution leads to an observed J close to zero. The steric properties of I, 1 and their derivatives [μ-2,2'-P(Ph)AuCl-{1-(1'-1',2'-closo-CBH)-1,2-closo-CBH}] (2) and [μ-2,2'-P(Et)AuCl-{1-(1'-1',2'-closo-CBH)-1,2-closo-CBH}] (3) have been assessed by Tolman cone angle and percent buried volume calculations, from which it is concluded that the bis(carboranyl)phosphines I and 1 are comparable to PCy in their steric demands. The selenides [μ-2,2'-P(Ph)Se-{1-(1'-1',2'-closo-CBH)-1,2-closo-CBH}] (4) and [μ-2,2'-P(Et)Se-{1-(1'-1',2'-closo-CBH)-1,2-closo-CBH}] (5) have also been prepared and characterised. The J coupling constants for 4 and 5 are the largest reported so far for carboranylphosphine selenides and indicate that I and 1 are very weakly basic.

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“…The simplest bis(carborane), namely 1,1 0 -bis(ortho-carborane), formally [1-(1 0 -1 0 ,2 0closo-C 2 B 10 H 11 )-1,2-closo-C 2 B 10 H 11 ] (Dupont & Hawthorne, 1964), consists of two ortho-carborane cages linked by a C1-C1 0 bond (Man et al, 2014). Some chemistry of 1,1 0bis(ortho-carborane) has been reported (see, for example, Hawthorne et al, 1971;Yanovsky et al, 1979;Doi et al, 1984;Long et al, 1984;Behnken et al, 1985;Getman et al, 1990Getman et al, , 1992Harwell et al, 1997;Ellis et al, 2010a;Thiripuranathar et al, 2015;Yao et al, 2015;Martin et al, 2015), but only one of these reports (Ellis et al, 2010a) is concerned with expansion of (one of) the cages to 13 vertices.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and crystal structures of theracemicandmesoforms of [1-{1′-4′-cyclopentadienyl-4′-cobalta-1′,12′-dicarba-closo-dodecaboranyl(10)}-4-cyclopentadienyl-4-cobalta-1,12-dicarba-closo-dodecaborane(10)], the former as its tetrahydrofuran disolvate

et al. 2015

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Both rac-[1-(1'-4'-Cp-4',1',12'-closo-CoC2B10H11)-4-Cp-4,1,12-closo-CoC2B10H11]·2THF (Cp is cyclopentadienyl and THF is tetrahydrofuran) or [Co2(C5H5)2(C4H22B20)]·2C4H8O, (1), and meso-[1-(1'-4'-Cp-4',1',12'-closo-CoC2B10H11)-4-Cp-4,1,12-closo-CoC2B10H11] or [Co2(C5H5)2(C4H22B20)], (2), were prepared by thermolysis of a rac/meso mixture of the precursor species [1-(1'-4'-Cp-4',1',6'-closo-CoC2B10H11)-4-Cp-4,1,6-closo-CoC2B10H11] and were separated, spectroscopically characterized and studied crystallographically. Cage C-atom identification was accomplished by both the vertex-to-centroid distance and boron-hydrogen distance methods, and, in both cases, the structure established crystallographically is fully consistent with the spectroscopic data. Both the rac-(1) and meso-(2) forms share the same overall conformation (Co-C-C'-Co' ca 136°) and show clear evidence of intramolecular steric crowding resulting in tilted cyclopentadienyl ligands.

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Definitive crystal structure of 1,1′-bis[1,2-dicarba-closo-dodecaborane(11)]

Abstract: In the title compound, the two {1,2-closo-C2B10H11} cages are linked across a centre of inversion with a C—C distance of 1.5339 (11) Å. By careful analysis of the structure, it is established that the non-linking cage C atom is equally disordered over cage vertices 2 and 3.

Cited by 12 publications

References 15 publications

Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)

Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)

Large, weakly basic bis(carboranyl)phosphines: an experimental and computational study

Synthesis and crystal structures of theracemicandmesoforms of [1-{1′-4′-cyclopentadienyl-4′-cobalta-1′,12′-dicarba-closo-dodecaboranyl(10)}-4-cyclopentadienyl-4-cobalta-1,12-dicarba-closo-dodecaborane(10)], the former as its tetrahydrofuran disolvate

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