%0 DATA
%A Beatriz, Calvo
%A Ramón, Macías
%A Maria
Jose, Artigas
%A Fernando J., Lahoz
%A Luis A., Oro
%D 2013
%T Reactions of 11-Vertex
Rhodathiaboranes with HCl:
Synthesis and Reactivity of New Cl-Ligated Clusters
%U https://acs.figshare.com/articles/dataset/Reactions_of_11_Vertex_Rhodathiaboranes_with_HCl_Synthesis_and_Reactivity_of_New_Cl_Ligated_Clusters/2454979
%R 10.1021/ic301715n.s002
%2 https://ndownloader.figshare.com/files/4097659
%K PPh 3
%K 2Ph
%K PR 3
%K PMe
%K PS
%K PSH
%K HCl
%K CO
%K DFT
%K Cl
%K cluster
%X Reactions of [8,8,8-(H)(PPh_{3})_{2}-9-(Py)-*nido*-8,7-RhSB_{9}H_{9}] (**1**),
[1,1-(PPh_{3})_{2}-3-(Py)-*closo*-1,2-RhSB_{9}H_{8}] (**2**), and [1,1-(CO)(PPh_{3})-3-(Py)-*closo*-1,2-RhSB_{9}H_{8}] (**4**), where Py = Pyridine, with HCl to give the Cl-ligated
clusters, [8,8-(Cl)(PPh_{3})-9-(Py)-*nido*-8,7-RhSB_{9}H_{9}] (**3**) and [8,8,8-(Cl)(CO)(PPh_{3})-9-(Py)-*nido*-8,7-RhSB_{9}H_{8}] (**5**), have recently demonstrated the remarkable *nido*-to-*closo* redox flexibility and bifunctional
character of this class of 11-vertex rhodathiaboranes. To get a sense
of the scope of this chemistry, we report here the reactions of PR_{3}-ligated analogues, [8,8,8-(H)(PR_{3})_{2}-9-(Py)-*nido*-8,7-RhSB_{9}H_{9}],
where PR_{3} = PMePh_{2} (**6**), or PPh_{3} and PMe_{3} (**7**); and [1,1-(PR_{3})_{2}-3-(Py)-*closo*-1,2-RhSB_{9}H_{8}], where PR_{3} = PPh_{3} and PMe_{3} (**8**), PMe_{3} (**9**) or PMe_{2}Ph (**10**), with HCl to give Cl-ligated clusters. The results
demonstrate that in contrast to the PPh_{3}-ligated compounds, **1**, **2**, and **3**, the reactions with **6**–**10** are less selective, giving rise to
the formation of mixtures that contain monophosphine species, [8,8-(Cl)(PR_{3})-9-(Py)-*nido*-8,7-RhSB_{9}H_{9}], where PR_{3} = PMe_{3} (**11**), PMe_{2}Ph (**12**), or PMePh_{2} (**15**), and bis-ligated derivatives, [8,8,8-(Cl)(PR_{3})_{2}-9-(Py)-*nido*-8,7-RhSB_{9}H_{9}],
where PR_{3} = PMe_{3} (**13**) or PMe_{2}Ph (**14**). The {RhCl(PR_{3})}-containing
compounds, **3**, **11**, **12**, and **15**, are formally unsaturated 12 skeletal electron pair (sep)
clusters with *nido*-structures. Density functional
theory (DFT) calculations demonstrate that the *nido*-structure is more stable than the predicted *closo*-isomers. In addition, studies have been carried out that involve
the reactivity of **3** with Lewis bases. Thus, it is reported
that **3** interacts with MeCN in solution, and it reacts
with CO and pyridine to give the corresponding Rh-L adducts, [8,8,8-(Cl)(L)(PPh_{3})-9-(Py)-*nido*-8,7-RhSB_{9}H_{9}], where L = CO (**5**) or Py (**20**). On the
other hand, the treatment of **3** and **5** with
Proton Sponge (PS) promotes the abstraction of HCl, as [PSH]Cl, from
the *nido*-clusters, and the regeneration of the parent *closo*-species, completing two new stoichiometric cycles
that are driven by Brønsted acid/base chemistry.