Closo-to-arachno redox flexibility in metallaheteroboranes may be viewed as a metal-to-ligand cooperative action with application in catalysis. The treatment of [PSH][arachno-4-SB(8)H(11)] with [RhCl(PPh(3))(3)] affords, after chromatography, three new 10-vertex rhodathiaboranes, [2,2,2-(H)(PPh(3))(2)-closo-2,1-RhSB(8)H(8)] (3), [6,6,9-(PPh(3))(3)-arachno-6,5-RhSB(8)H(9)] (4) and [2,2,2-(Cl)(H)(PPh(3))-6-(PPh(3))-closo-2,1-RhSB(8)H(7)] (5). 3 reacts quantitatively with PPh(3) to form 4, which, in turn, reacts with chlorinated solvents to give the chloro-ligated cluster 5. Kinetic studies demonstrate that the reaction of 3 with PPh(3) obeys a second-order rate law, with an associative mechanism. The Lewis acidity of 3 is quite remarkable, and, given its closo-to-arachno structural and electronic response, this cluster is expected to exhibit a rich chemistry.
New 10-vertex rhodathiaboranes are reported to exhibit reversible reaction chemistry leading to the formation of stoichiometric cycles driven by oxidation/reduction chemistry of the polyhedral boron-based clusters with ethelyne and dihydrogen.
Dedicated to Professor Thomas P. Fehlner on his 75th birthday. He has been a superb mentor of many scientists around the world working on "inorganometallic chemistry". Keywords:The reaction between [arachno-6-SB 9 H 12 ] À and [IrCl(CO)(PMe 3 ) 2 ] affords the previously reported 11-vertex cluster, [8,8,(PMe 3 ) 2 -arachno-8,7-IrSB 9 H 10 ] (4), and small amounts of the new 10-vertex iridathiaborane [9,9,9,(H)(PMe 3 ) 2 -arachno-9,6-IrSB 8 H 10 ] (5). Alternatively, a rational synthesis of iridathiadecaboranes is effected from the reaction of the 9-vertex anion [arachno-4-SB 8 H 11 ] À with [MCl(CO)(PPh 3 ) 2 ], to afford new CO-ligated 10-vertex metallathiaboranes of formulation, [9,9,9,(H)(PPh 3 ) 2 -arachno-9,6-MSB 8 H 10 ], where M ¼ Rh (6) and Ir (7), in useful yields of 61% and 60% respectively. Treatment of the 11-vertex rhodathiaborane, [8,8-(PPh 3 ) 2 -8,7-nido-RhSB 9 H 10 ] (1) with nBuLi, followed by addition of [IrCl(CO)(PMe 3 ) 2 ] affords the 12-vertex iridarhodathiaborane, [1,2-(m-CO)-1,1,2-(PMe 3 ) 3 -2-(PPh 3 )-closo-1,2-IrRhSB 9 H 9 ] (8) in low yield (0.7%). The 10-vertex metallathiaboranes, 5, 6 and 7, and the bimetallic 12-vertex cluster, 8, have been characterized by multinuclear NMR spectroscopy. In addition, the molecular structures of compounds 5, 6, and 8 have been studied by X-ray diffraction.
It has been demonstrated that the reaction of [2,2,2-(H)(PPh3)2-closo-2,1-RhSB8H8] () with PPh3 affords the boron substituted rhodathiaborane-PPh3 adduct, [6,6-(PPh3)2-9-(PPh3)-arachno-6,5-RhSB8H9] (). Building upon this reaction, we report herein that the 10-vertex hydridorhodathiaborane reacts with the Lewis bases, PCy3, py, 2-Mepy, 2-Etpy, 3-Mepy and 4-Mepy to form the rhodathiaborane-ligand adducts, [6,6-(PPh3)2-9-(L)-arachno-6,5-RhSB8H9], where L = PCy3 (), 2-Mepy (), 2-Etpy (), py (), 3-Mepy () or 4-Mepy (), and [8,9-μ-(H)-9-(PPh3)2-8-(L)-arachno-9,6-RhSB8H8], where L = py (), 3-Mepy () or 4-Mepy (). The selectivity of the reactions depended on the nature of the entering Lewis bases, affording the 6,5-isomers, , , and as single products for PPh3, PCy3, 2-Mepy and 2-Etpy; and mixtures of the 6,5-/9,6-regioisomers, /, / and / for py, 3-Mepy and 4-Mepy, respectively. The molecular structures of both regioisomers were characterized by X-ray diffraction analysis for the 6,5-isomers, and , and for the 9,6-isomers, and . Variable temperature NMR studies of the reaction between and PPh3 or 2-Mepy demonstrated that at low temperatures there is formation of the 9,6-species that subsequently isomerizes to the 6,5-regioisomer, indicating that for the more sterically hindered Lewis bases, PPh3, 2-Mepy and PCy3, the latter isomer is more stable and accessible through an intramolecular {Rh(PPh3)2} vertex flip. The formation of both isomers with py, 3-Mepy and 4-Mepy indicates that the kinetic and thermodynamic energies of the 6,5 and 9,6 rhodathiaborane-ligand adducts are similar for these Lewis bases. Lewis base bonding to exo-polyhedral boron vertices results in a change of the metal coordination from pseudo-octahedral Rh(iii) in to pseudo-square planar Rh(i) in the adducts. The chemistry described here highlights the remarkable structural flexibility of these polyhedral boron-containing compounds, their modular architecture and their easy postsynthetic modification.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.