000118955 001__ 118955
000118955 005__ 20240319081010.0
000118955 0247_ $$2doi$$a10.1021/acs.inorgchem.2c01902
000118955 0248_ $$2sideral$$a130092
000118955 037__ $$aART-2022-130092
000118955 041__ $$aeng
000118955 100__ $$aCarmona, M.
000118955 245__ $$aActivation of H-H, HO-H, C(sp2)-H, C(sp3)-H, and RO-H bonds by transition-metal frustrated lewis pairs based onon M/N (M = Rh, Ir) couples
000118955 260__ $$c2022
000118955 5060_ $$aAccess copy available to the general public$$fUnrestricted
000118955 5203_ $$aReaction of the dimers (Cp*MCl)2(µ-Cl)2] (Cp* = 5-C5Me5) with Ph2PCH2CH2NC(NH(p-Tolyl))2 (H2L) in the presence of NaSbF6 affords the chlorido complexes Cp*MCl(¿2N, P-H2L)]SbF6] (M = Rh, 1; Ir, 2). Upon treatment with aqueous NaOH, solutions of 1 and 2 yield the corresponding complexes Cp*M(¿3N, N', P-HL)]SbF6] (M = Rh, 3; Ir, 4) in which the ligand HL presents a fac ¿3N, N', P coordination mode. Treatment of THF solutions of complexes 3 and 4 with hydrogen gas, at room temperature, results in the formation of the metal hydrido-complexes Cp*MH(¿2N, P-H2L)]SbF6] (M = Rh, 5; Ir, 6) in which the N(p-Tolyl) group has been protonated. Complexes 3 and 4 react with deuterated water in a reversible fashion resulting in the gradual deuteration of the Cp* group. Heating at 383 K THF/H2O solutions of the complexes 3 and 4 affords the orthometalated complexes Cp*M(¿3C, N, P-H2L-H)]SbF6] M = Rh, 7; Ir, 8, H2L-H = Ph2PCH2CH2NC(NH(p-Tolyl))(NH(4-C6H3Me))], respectively. At 333 K, complexes 3 and 4 react in THF with methanol, primary alcohols, or 2-propanol giving the metal-hydrido complexes 5 and 6, respectively. The reaction involves the acceptorless dehydrogenation of the alcohols at a relatively low temperature, without the assistance of an external base. The new complexes have been characterized by the usual analytical and spectroscopic methods including the X-ray diffraction determination of the crystal structures of complexes 1-5, 7, and 8. Notably, the chlorido complexes 1 and 2 crystallize both as enantiopure conglomerates and as racemates. Reaction mechanisms are proposed based on stoichiometric reactions, nuclear magnetic resonance studies, and X-ray crystallography as well as density functional theory calculations. © 2022 The Authors. Published by American Chemical Society.
000118955 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E05-20R$$9info:eu-repo/grantAgreement/ES/MCIU/RED2018-102574-T$$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00
000118955 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000118955 590__ $$a4.6$$b2022
000118955 592__ $$a0.997$$b2022
000118955 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 42 = 0.119$$c2022$$dQ1$$eT1
000118955 593__ $$aChemistry (miscellaneous)$$c2022$$dQ1
000118955 593__ $$aPhysical and Theoretical Chemistry$$c2022$$dQ1
000118955 593__ $$aInorganic Chemistry$$c2022$$dQ1
000118955 594__ $$a8.0$$b2022
000118955 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000118955 700__ $$aPérez, R.
000118955 700__ $$0(orcid)0000-0003-4568-2204$$aFerrer, J.$$uUniversidad de Zaragoza
000118955 700__ $$0(orcid)0000-0002-8845-0174$$aRodríguez, R.
000118955 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, V.
000118955 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, F. J.
000118955 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, P.
000118955 700__ $$0(orcid)0000-0003-4196-5856$$aCarmona, D.
000118955 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000118955 773__ $$g61, 33 (2022), 13149 - 13164$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000118955 8564_ $$s5581429$$uhttps://zaguan.unizar.es/record/118955/files/texto_completo.pdf$$yVersión publicada
000118955 8564_ $$s3006427$$uhttps://zaguan.unizar.es/record/118955/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000118955 909CO $$ooai:zaguan.unizar.es:118955$$particulos$$pdriver
000118955 951__ $$a2024-03-18-15:04:35
000118955 980__ $$aARTICLE