Vibrational Spectrum and Electronic Structure of the [B11H11]2–Dianion

Kononova, Elena G.; Leites, L. A.; Bukalov, S. S.; Pisareva, I. V.; Chizhevsky, I. T.; Kennedy, John D.; Bould, Jonathan

doi:10.1002/ejic.200700461

Cited by 16 publications

(15 citation statements)

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“…The reactions of picoline-ligated hydridorhodathiaboranes (3-5) with C 2 H 4 and CO in this report resemble those found for the pyridine analog, 2, giving products of ligand substitution and cluster dehydrogenation (12)(13)(14)(15)(16)(17)(18)(19). These reactions nicely illustrate the structural flexibility and chemical tunability of these 11-vertex clusters and demonstre that the parent rhodathiaborane, [8, ) 2 -nido-8,7-RhSB 9 H 10 ] (1), first reported in 1990, 4 is actually a rich source of organometallic chemistry.…”

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confidence: 68%

“…In a similar fashion to the reactions with ethylene, the treatment of these pyridine and picolineligated hydridorhodathiaboranes, 2-5, with carbon monoxide affords the products of hydrogen loss and PPh 3 substitution, [1,1-(CO)(PPh 3 )-3-(L)-1,2-RhSB 9 H 8 ], (17)(18)(19) As we can see, thermal dehydrogenation, and reactions with CO and C 2 H 4 are convenient routes to the synthesis of 11-vertex rhodathiaboranes with closo / isonido-cluster geometries, which bear different exo-polyhedral ligands either at the metal centre or the boron-3 vertex. Thus, these reactions broaden the scope of the substitution chemistry in this system, allowing a systematic tuning of their reactivity.…”

Section: Studies Of Reactivitymentioning

confidence: 99%

“…In the case of compound 8, this distance at 2.562(6) Å is outside this limit. This elongation results in the formation of a pseudo-square open face that is a structural feature common in closo- 11-vertex clusters, 19 which represent intermediates along the structural continuum from closo to nido. 16,20 Figure 4 Molecular structure of [1,1-(PPh 3 ) 2 -3-(2-Me-NC 5 H 4 )-closo-1,2-RhSB 9 H 8 ] (9).…”

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Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

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The reaction between pyridine and [8, (17, 18, 19). These series of  2 -C 2 H 4 -and CO-ligated 11-vertex isonido / closorhodathiaboranes result from the substitution of one PPh 3 ligand by ethylene or CO together with H 2 loss and a concomitant nido-to-closo / isonido-cluster structural transformation. The reactivity of 3-5 with propene, 1-hexene and cyclohexene in a hydrogen atmosphere is also reported and compared with the reactivity of the pyridine-ligated analogue, [8,8,8-(H)(PPh 3 ) 2 -9-(NC 5 H 5 )-nido-8,7-RhSB 9 H 9 ] (2). Low temperature NMR studies have allowed the characterization of intermediates which undergo inter-and intramolecular exchange processes, depending on the nature of the N-heterocyclic ligand. The CO ligand enhances the non-rigidity of the cluster, opening mechanisms of H 2 loss from the clusters.) 3MANUSCRIPT TEXT

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Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

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“…structural data (measured or calculated interatomic distances), chemical behaviour, and, in some cases, fluxional behavior in solution, has been taken to indicate that they do not necessarily possess a formal closed deltahedral structure but the four long connectivities are essentially nonbonding, so that the species have effectively two five-membered open faces reminiscent of a 'remote arachno' configuration (e.g. 35A and 35B) [37]. The term quasiclosohas been coined for such structures.…”

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Nomenclature for boranes and related species (IUPAC Recommendations 2019)

Beckett

Brellochs²,

Chizhevsky

et al. 2019

Pure and Applied Chemistry

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An appraisal of the current IUPAC recommendations for the nomenclature of boranes and related systems has been undertaken. New developments in the field have been investigated and existing nomenclature systems have been adapted to accommodate these new developments. The principal areas considered are stoichiometric and structural nomenclature (including heteroatom and metal-atom subrogation, as well as substitution of hydrogen), conjoined-cage species, supra-icosahedral systems, and sub-icosahedral non-standard structures. Elements of substitutive, additive, and replacement nomenclature systems have been integrated into individual names to address contentious problems in boron nomenclature that have been around for a long time.

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“…Results suggest that because the polyhedron do not consist of deltahedral faces only, the cluster does not have a genuine closo structure. 7 Computational methods have been used to examine the most thermodynamically favoured sub-cluster combinations for two-vertex sharing nido:nido-, arachno:nidoand arachno:arachno-macropolyhedral borane clusters. 8 The synthesis of the facially fused macropolyhedral borane fac-[B 20 H 18 ] 2À has been achieved through an oxidative coupling of closo-[B 10 H 10 ] 2À ions.…”

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Boron

Johnson

2008

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter reviews the literature reported in 2007 concerning the chemistry of the boron, and focuses on those articles and publications that have appeared in 'high impact' journals. Because of the breadth of research into the area of boron chemistry, boron is again handled separate from the other elements of Group 13. The text excludes much material or technological chemistry unless original, fundamental or notable for other reasons. Due to space limitations this review is not exhaustive and the author apologises in advance that not all published work can be covered to the same extent. Boron highlightsDuring 2007 the chemistry of boryl and borylene complexes has continued to expand and remarkable progress has been made. Special mention should be made of the work of Robinson et al. in the development and synthesis of Lewis base stabilised B-B and BQB systems. Advances in the chemistry of B-N cyclic compounds have also been noteworthy over 2007 and the work of Norman et al. and Himmel et al. take centre stage in this. The standard and quality of work that exists in the boron community continues to be exceptional and long may it continue. Polyhedral boranesIn a very elegant piece of chemistry Robinson and co-workers have described the synthesis of N-heterocyclic carbene (NHC) stabilised examples of a diborane hydride (1) and the first example of a neutral diborene (2) containing a BQB bond, by reduction of NHC borane adducts, (NHC) Á BBr 3 and (NHC) Á BH 3 with KC 8 . 1 Surface scattering of a diborane matrix (10 K) has been used to generate the monobridged diboryl radical B 2 H 5 , which has been studied using IR spectroscopy to elucidate the structure. 2 The structures and energetics of cyclic boron-aluminium hydrides BAl 2 H n m (n = 3-6, m = À2 to +1) have been investigated using computational methods.

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Vibrational Spectrum and Electronic Structure of the [B₁₁H₁₁]^2–Dianion

Cited by 16 publications

References 32 publications

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

Nomenclature for boranes and related species (IUPAC Recommendations 2019)

Boron

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