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- Title
Differential Reactivity of [TpRu(k²P,N-iPr<sub>2</sub>PXPy)Cl] (X = NH, S) Bearing Hemilabile Coligands Towards NaBAr<sup>F</sup><sub>4</sub>, Lithium Acetylide, and Acetylenes.
- Authors
Singh, Vinay K.; Puerta, M. Carmen; Valerga, Pedro
- Abstract
In contrast with [TpRu(k²P,N-iPr2PNHPy)Cl] (1a, Tp = trispyrazolylborate), [TpRu(k²P,N-iPr2PSPy)Cl] (1b) reacts with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF4) in fluorobenzene under nitrogen to afford the dinuclear complex [{TpRu(k²P,N-iPr2PSPy)}2(µ-Cl)][BArF4] (1b'). Through diverse synthetic strategies, a series of neutral acetylides [TpRu(C≡CR)(k²P,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)(k²P,NiPr2PNHPy)]+ [X = NH; R = Ph (3a), SiMe3 (3b); X = S; R = Ph (3c), p-C6H4Br (3d)] and [TpRu(=C=CH2)(k²P,N-iPr2PNHPy)]+(3e), and a cationic k²-alkyne complex [TpRu(k²- HC≡CCOOMe)(k²P,N-iPr2PSPy)][BArF4] have been efficiently synthesized from 1a and 1b. The methoxy(methyl)- carbene complexes [TpRu{=C(OMe)CH3}(k²P,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.
- Subjects
LIGANDS (Chemistry); LITHIUM; ACETYLIDES; RUTHENIUM compounds; ALKYNES; ACETYLENE
- Publication
European Journal of Inorganic Chemistry, 2015, Vol 2015, Issue 10, p1811
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201500082