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

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

Multi-pyridine decorated Fe(ii) and Ru(ii) complexes by Pd(0)-catalysed cross couplings: new building blocks for metallosupramolecular assemblies

Eight metal complexes of the type [M(tpy)2]2+ (tpy = 2,2′:6′,2′′-terpyridine) featuring four pendant pyridine rings are reported and characterised by NMR, MS, absorption spectroscopy and electrochemical methods. Palladium-mediated Suzuki and Sonogashira cross-coupling reactions were performed on both free 4′-(3,5- dibromophenyl)-tpy and its Ru(ii) complex in good yields. The ready N-alkylation of the pendant pyridyl units has significant influence on the absorption and electrochemical reduction of the complexes, processes which are localised on the periphery and leaves the [Ru(tpy)2]2+ core essentially unaffected. The binding of metal ions by the free pyridines is also demonstrated as means of assembling larger ordered non-covalent structures. This journal i