B‐Substituted (Arene)ruthenacarborane–Sulfonium, –Thioether and–Mercaptan Complexes: Mild Single and Double Dealkylation and Structural Implications in the Antipodal Distance

Abstract

Reactions of [RuCl 2 (η 6 -arene)] 2 (arene = benzene, p-cymene) with nido- [7-R-10-L-7,8-C 2 B 9 H 9 ] -in THF at room temperature for 3 d give the (arene)ruthenacarborane complexes

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me2-X-SMe2-7,8-nido-C2B9H8]− (X = 9 and 10)

“…11 B­{ 1 H} NMR spectra and boron assignment for complexes 2 and 5 are represented on Figure . The most significant effect appears in B9 resonances difference (Δδ = 3.3 ppm) antipodal to the metal atom and it is known in the literature as the antipodal effect (AE) . The second significant effect apparent from Figure is the resonances difference (Δδ = 2.3 ppm) between Me 2 S–B­(7) boron atoms.…”

Unusual Cationic Tris(Dimethylsulfide)-Substituted closo-Boranes: Preparation and Characterization of [1,7,9-(Me2S)3-B12H9] BF4 and [1,2,10-(Me2S)3-B10H7] BF4

“…24,25 Indeed, apparently stepwise double demethylations have been observed in these cases, resulting first in thioether-and subsequently in mercaptansubstituted ruthenacarboranes…”

Unusual cationic rhodathiaboranes: synthesis and characterization of [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H10]+and [1,3-μ-(H)-1,1-(PR3)2-3-(Py)-isonido-1,2-RhSB9H8]+

“…Since the yields of these neutral 11-vertex rhodathiaboranes are generally good, this is a convenient entry into the area of polyhedral boron-containing cations which is scarcely explored with only a small number of reported cationic boranes and metallaheteroboranes. [39][40][41][42][43][44][45][46][57][58][59][60][61][62][63] It is important to recall that the majority of reported cationic metallaheteroboranes generally contain charge-compensating ligands; [41][42][43][44][45][46] and the number of cationic polyhedral boron clusters formed by simple protonation is very small indeed. 39,40 The herein reported reactions with TfOH together with previous results with HCl 36,64 give an overall view of the reactivity of this family of rhodathiaboranes with Brønsted acid (Scheme 4).…”

“…40 In fact, the large majority of cationic metallaheteroboranes are based on charge-compensated heteroborane fragments, which act as face-bound ligands and which are somewhat different in nature from the polyhedral cations we describe in the present work. [41][42][43][44][45][46] Herein, we build upon protonation reactions of the abovepresented series of 11-vertex rhodathiaboranes, reporting a unique set of polyhedral cations that represent some of the few examples of cationic boron-based clusters of any type.…”