000063448 001__ 63448
000063448 005__ 20200221144339.0
000063448 0248_ $$2sideral$$a102308
000063448 037__ $$aART-2016-102308
000063448 041__ $$aeng
000063448 100__ $$aLuaces, Susana
000063448 245__ $$aPostsynthetic modifications of [2,2,2-(H)(PPh3)2-closo-2,1-RhSB8H8] with lewis bases: cluster modular tuning
000063448 260__ $$c2016
000063448 5060_ $$aAccess copy available to the general public$$fUnrestricted
000063448 5203_ $$aIt has been demonstrated that the reaction of [2,2,2-(H)(PPh3)2-closo-2,1-RhSB8H8] (1) with PPh3 affords the boron substituted rhodathiaborane–PPh3 adduct, [6,6-(PPh3)2-9-(PPh3)-arachno-6,5-RhSB8H9] (2). Building upon this reaction, we report herein that the 10-vertex hydridorhodathiaborane 1 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 (3), 2-Mepy (4), 2-Etpy (5), py (6a), 3-Mepy (7a) or 4-Mepy (8a), and [8,9-µ-(H)-9-(PPh3)2-8-(L)-arachno-9,6-RhSB8H8], where L = py (6b), 3-Mepy (7b) or 4-Mepy (8b). The selectivity of the reactions depended on the nature of the entering Lewis bases, affording the 6,5-isomers, 2, 3, 4 and 5 as single products for PPh3, PCy3, 2-Mepy and 2-Etpy; and mixtures of the 6,5-/9,6-regioisomers, 6a/6b, 7a/7b and 8a/8b 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, 3 and 4, and for the 9,6-isomers, 7b and 8b. Variable temperature NMR studies of the reaction between 1 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 1 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.
000063448 536__ $$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/CSD2009-00050$$9info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio/CSD2006-0015$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2009-10132$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-32095
000063448 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000063448 590__ $$a4.029$$b2016
000063448 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 46 = 0.152$$c2016$$dQ1$$eT1
000063448 592__ $$a1.229$$b2016
000063448 593__ $$aInorganic Chemistry$$c2016$$dQ1
000063448 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000063448 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vincenzo
000063448 700__ $$aArtigas, María José
000063448 700__ $$aLahoz, Fernando J.
000063448 700__ $$aOro, Luis A.
000063448 700__ $$aMacias, Ramón
000063448 773__ $$g45, 20 (2016), 8622-8636$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000063448 8564_ $$s2147123$$uhttps://zaguan.unizar.es/record/63448/files/texto_completo.pdf$$yPostprint
000063448 8564_ $$s107466$$uhttps://zaguan.unizar.es/record/63448/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000063448 909CO $$ooai:zaguan.unizar.es:63448$$particulos$$pdriver
000063448 951__ $$a2020-02-21-13:49:08
000063448 980__ $$aARTICLE