Half-sandwich complexes of osmium containing guanidine-derived ligands?

Dalton Transactions Pub Date: 2020-09-22 DOI: 10.1039/D0DT02713H

Abstract

Pyridinyl- and phosphano-guanidino complexes of formula [(η6-p-cymene)OsCl(H2L)][SbF6] (cymene = MeC6H4iPr; H2L = N,N′-bis(p-Tolyl)-N′′-(2-pyridinylmethyl)guanidine, H2L1 (1) and N,N′-bis(p-Tolyl)-N′′-(2-diphenylphosphanoethyl)guanidine, H2L2 (2)) have been prepared from the dimer [{(η6-p-cymene)OsCl}2(μ-Cl)2] and H2L in the presence of NaSbF6. Treatment of complex 2 with HCl renders the phosphano–guanidinium complex [(η6-p-cymene)OsCl2(H3L2)][SbF6] (3). Compounds 1 and 2 react with AgSbF6 rendering the cationic aqua complexes [(η6-p-cymene)Os(H2L)(OH2)][SbF6]2 (H2L = H2L1 (4), H2L2 (5)). Addition of monodentate ligands L to compound 4 affords complexes of formula [(η6-p-cymene)Os(H2L1)L][SbF6]2 (L = py (6), 4-(NHMe)py (7), CO (8), P(OMe)3 (9)). Treatment of complexes 4 and 5 with NaHCO3 renders the monocationic complexes [(η6-p-cymene)Os(κ3N,N′,N′′-HL1)][SbF6] (10) and [(η6-p-cymene)Os(κ3N,N′,P-HL2)][SbF6] (11), respectively, in which the HL ligand adopts a fac-κ3 coordination mode. The new complexes have been characterised by analytical and spectroscopic means, including the determination of the crystal structures of the compounds 1–4, 6, 8, and 11, by X-ray diffractometric methods. The phosphano–guanidino complexes 2 and 5 exhibit a temperature dependent fluxional process in solution. The new 18 electron complexes 1, 2, 6, and 8–10 are active catalysts for the Friedel–Crafts reaction between trans-β-nitrostyrene and N-methyl-2-methylindole. Conversions greater than 90% were obtained. Proton NMR studies support a mechanism involving the Br?nsted-acid activation of trans-β-nitrostyrene through the NH functionalities of the coordinated guanidine ligands.

Graphical abstract: Half-sandwich complexes of osmium containing guanidine-derived ligands
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