RT journal article
T1 Differential Reactivity of [TpRu(κ2P,N-iPr2PXPy)Cl] (X = NH, S) Bearing Hemilabile Coligands Towards NaBArF 4, Lithium Acetylide, and Acetylenes
A1 K. Singh, Vinay
A1 Puerta Vizcaino, María del Carmen
A1 Valerga Jiménez, Pedro Sixto
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
K1 Ruthenium
K1 Alkyne ligands
K1 Vinylidene ligands
K1 Carbene ligands
K1 Acetylides
AB 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.
YR 2015
FD 2015-02
LK http://hdl.handle.net/10498/20446
UL http://hdl.handle.net/10498/20446
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 15-nov-2026