Reactions of 11-Vertex Rhodathiaboranes with HCl: Synthesis and Reactivity of New Cl-Ligated Clusters

Calvo, B.; Macı́as, Ramón; Artigas, M.; Lahoz, Fernando J.; Oro, Luis A.

doi:10.1021/ic301715n

Cited by 9 publications

(12 citation statements)

References 39 publications

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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.…”

supporting

confidence: 70%

“…6,12 Based on the results summarized above, we logically aimed to change the pyridine substituent at the boron vertices. Herein, we report the reactions of the parent rhodathiaborane, 1, with the methylpyridine isomers (picolines), 2-Me-NC 5 H 4 , 3-Me-NC 5 H 4 and 4-Me-NC 5 H 4 .…”

Section: Scheme 1 Reactivity Of Compounds 1 and 2 With Lewis Bases: Smentioning

confidence: 99%

“…15 Moreover, in some 11-vertex nido-rhodathiaboranes, it has been calculated that a metal-thiaborane interaction change from a sulfur-metal-hydride trans-arrangement to a boronmetal-hydride trans-configuration can have an energy cost as high as 12 kcal/mol. 12,16 Figure 2 Representation of the 11 B NMR spectra of 2-4 and 7. Hatched lines connect equivalent positions.…”

Section: Synthesis and Characterization Of Picoline-ligated 11-vertexmentioning

confidence: 99%

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Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

et al. 2014

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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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confidence: 70%

Section: Scheme 1 Reactivity Of Compounds 1 and 2 With Lewis Bases: Smentioning

confidence: 99%

Section: Synthesis and Characterization Of Picoline-ligated 11-vertexmentioning

confidence: 99%

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Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

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“…5 As expected, the Rh-P distances in the chelate are significantly shorter than in the derivative with monodentate phosphines. The structural effect of the chelating ligand also manifests in the smaller P(1)-Rh(1)-P(2) angle [85.015 (19) vs. 96.27 (4)]. …”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…Rh ( 4 The angle between the {S(7)Rh(8)B(9)} and {S(7)B(2)B(5)B(9)} planes, θ, is appropriate to examine for intermediacy of structure between conventionally nido compounds and closocages. 4 This angle is virtually zero in 11-vertex octadecahedral clusters such as compound 2, and in compound 3, the angle is 45°, close to the value of 48°, found in its isoelectronic neutral counterpart [8,8-(η 2 -dppp)-nido-8,7-RhSB 9 H 10 ], which has been structurally well characterized by X-ray diffraction analysis.…”

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[1,1-(η²-dppe)-3-(NC₅H₅)-closo-1,2-RhSB₉H₈]: conformational lability and reactivity with H₂ upon protonation

et al. 2015

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Metallaheteroboranes are versatile compounds that can be conveniently modified and eventually tailored by ligand modification at either the metal centre or the boron vertices. Recently, we have discovered that protonation of some rhodathiaboranes affords cationic clusters with interesting reaction chemistry. In order to tune the reactivity of some of these polyhedral boron-based compounds, we have prepared air-stable orange [1,1-(η(2)-dppe)-3-(NC5H5)-closo-1,2-RhSB9H8] (2) by the treatment of the known hydridorhodathiaborane [8,8,8-(H)(PPh3)2-9-(NC5H5)-nido-8,7-RhSB9H9] (1) with dppe. The new 11-vertex rhodathiaborane, 2, reacts readily with triflic acid (TfOH) in CH2Cl2 to give orange cationic [8,8-(η(2)-dppe)-9-(NC5H5)-nido-8,7-RhSB9H9](+) (3). VT NMR experiments have allowed the characterization of a structural closo ↔ nido tautomerism, which involves hapticity changes in the ligation of the {SB9H9-(NC5H5)} moiety to the {Rh(dppe)} fragment, with the proton moving between the Rh(1)-B(3) and the B(9)-B(10) edges of the closo- and nido-isomers, respectively. The proton enhances the stereochemical non-rigidity and Lewis acidity of 3 versus the neutral 2. This modification of the chemical and structural basis permits the efficient heterolytic splitting of the H-H bond, leading to the formation of new hydridorhodathiaborane isomers [8,8,8-(H)(η(2)-dppe)-μ-8,9-(H)-9-(NC5H5)-nido-8,7-RhSB9H10](+) ()4 that are in equilibrium with the reactants, H2 and 3.

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Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

et al. 2017

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Reactions of 11-Vertex Rhodathiaboranes with HCl: Synthesis and Reactivity of New Cl-Ligated Clusters

Cited by 9 publications

References 39 publications

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

[1,1-(η²-dppe)-3-(NC₅H₅)-closo-1,2-RhSB₉H₈]: conformational lability and reactivity with H₂ upon protonation

Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

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Reactions of 11-Vertex Rhodathiaboranes with HCl: Synthesis and Reactivity of New Cl-Ligated Clusters

Cited by 9 publications

References 39 publications

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

[1,1-(η2-dppe)-3-(NC5H5)-closo-1,2-RhSB9H8]: conformational lability and reactivity with H2 upon protonation

Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

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[1,1-(η²-dppe)-3-(NC₅H₅)-closo-1,2-RhSB₉H₈]: conformational lability and reactivity with H₂ upon protonation