Alkyne‐Promoted H₂Loss in a Metallaborane:Nido‐to‐ClosoCluster Transformation and sp CH Bond Oxidative Addition

Abstract

A sensitive cluster: The labile rhodathiaborane [(PPh(3))(2)(H)-nido-RhSB(9)H(9)(NC(5)H(5))] combines the redox and coordinative flexibility of the {(PPh(3))(2)(H)Rh} fragment with the capability of the 11-vertex rhodathiaborane cluster to undergo oxidative nido-to-closo transformations induced by coordination of alkynes to the metal centre, which leads to hydrogenation of the triple bond, dehydrogenation of the cluster and oxidative addition of sp C-H bonds.

Hydridorhodathiaboranes: Synthesis, Characterization, and Reactivity

“…Overall, this family of neutral and cationic 11-vertex rhodathiaboranes has revealed a rich chemistry that embraces: (i) nido-to-closo dehydrogenations, 9 (ii) dihydrogen promoted closo-to-nido transformations 6b,7 , (iii) oxidative addition of sp CH bonds, 10 (iv) proton-assisted H 2 activation 11 and (v) catalysis of hydrogenation and isomerization of olefins. 6b In these reactions, the clusters exhibit metal-borane collaboration through structural transformations that lead to metal-ligand hapticity changes.…”

Chemistry of Triple‐Decker Sandwich Complexes Containing Four‐Membered Open B2E2 Rings (E = S or Se)

“…The developments towards large numbers of metallaheteroboranes have gained a good deal of interest, owing to their utility in the preparation of high‐nuclearity clusters . Among them, group 9 metallaheteroboranes have received significant attention, due to their applications in catalysis , . For example, nido ‐rhodathiaborane [8,8,8‐(PPh 3 ) 2 H‐9‐(NC 5 H 5 )‐ nido ‐8,7‐RhSB 9 H 9 ] acts as a catalyst for the isomerization and hydrogenation of alkenes.…”

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

“…These rhodium units are reminiscent of 1, 6 which contains a {Rh(H)(PPh 3 ) 2 } fragment at the 8-position. Thus, for comparison, important interatomic distances and angles in 1, 3, 5, 13 and 14 are given in Table 2.…”