Differential Reactivity of [TpRu(κ2P,N-iPr2PXPy)Cl] (X = NH, S) Bearing Hemilabile Coligands Towards NaBArF 4, Lithium Acetylide, and Acetylenes

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Differential Reactivity of [TpRu(κ2P,N-iPr2PXPy)Cl] (X = NH, S) Bearing Hemilabile Coligands Towards NaBArF 4, Lithium Acetylide, and Acetylenes

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Title: Differential Reactivity of [TpRu(κ2P,N-iPr2PXPy)Cl] (X = NH, S) Bearing Hemilabile Coligands Towards NaBArF 4, Lithium Acetylide, and Acetylenes
Author: K. Singh, Vinay; Puerta Vizcaino, María del Carmen; Valerga Jiménez, Pedro Sixto
Departments: Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
xmlui.dri2xhtml.METS-1.0.item-source: European Journal of Inorganic Chemistry 2015, 1811–1818
Abstract: In contrast with [TpRu(κ2P,N-iPr2PNHPy)Cl] (1a, Tp = trispyrazolylborate), [TpRu(κ2P,N-iPr2PSPy)Cl] (1b) reacts with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF 4) in fluorobenzene under nitrogen to afford the dinuclear complex [{TpRu(κ2P,N-iPr2PSPy)}2(μ-Cl)][BArF4] (1b ). Through diverse synthetic strategies, a series of neutral acetylides [TpRu(C CR)(κ2P,N-iPr2PXHPy)] [X = NH; R = Ph (2a), SiMe3 (2b); X = S; R = Ph (2c), p-C6H4Br (2d), COOMe (2e)], cationic vinylidene complexes [TpRu(=C=CHR)(κ2P,NiPr2PNHPy)]+ [X = NH; R = Ph (3a), SiMe3 (3b); X = S; R = Ph (3c), p-C6H4Br (3d)] and [TpRu(=C=CH2)(κ2P,N-iPr2PNHPy)]+ (3e), and a cationic η2-alkyne complex [TpRu(η2- HC CCOOMe)(κ2P,N-iPr2PSPy)][BArF 4] have been efficiently synthesized from 1a and 1b. The methoxy(methyl)- carbene complexes [TpRu{=C(OMe)CH3}(κ2P,N-iPr2PXPy)]- [BPh4] [X = NH (5a), S (5b)] were isolated from the reactions of 1a and 1b with acetylene gas in the presence of NaBArF4 in methanol. The deprotonation of the cationic vinylidenes derived from 1b with KtBuO affords the corresponding neutral acetylide complexes, which undergo facile protonation with CF3SO3H to reproduce the cationic vinylidenes quantitatively.
Subject: Ruthenium ; Alkyne ligands ; Vinylidene ligands ; Carbene ligands ; Acetylides.
Handle: http://hdl.handle.net/10498/20446
Date: 2015-02

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