Abstract
The synthesis of a series of arene-osmium(II) complexes containing phosphinite-type ligands, namely, [OsCl2(η6-p-cymene){R2PO(CH2)nPh}] (R = Ph, n = 1 (4a), 2 (4b), 3 (4c); R = iPr, n = 1 (5a), 2 (5b), 3 (5c)) and [OsCl2(η6-benzene){iPr2PO(CH2)2Ph}] (7), is presented. All these compounds were characterized by elemental analysis and multinuclear NMR spectroscopy (31P{1H}, 1H and 13C{1H}), and the structure of [OsCl2(η6-p-cymene){Ph2PO(CH2)3Ph}] (4c) unequivocally confirmed through a single-crystal X-ray diffraction study. Attempts to generate the tethered species [OsCl2{η6:κ1(P)-C6H5(CH2)nOPR2}] by intramolecular exchange of the coordinated arene in 4-5a-c or 7, upon thermal or MW heating, failed.
Highlights
We recently described the preparation of the ruthenium(II)
The marked differences in reactivity found between the osmium complexes synthesized, i.e., 4-5a-c and 7, and their ruthenium counterparts can be ascribed to the higher activation energies associated to ligand substitution processes in osmium vs. ruthenium complexes, a fact well documented in the literature [16,17,18]
All manipulations were carried out under an inert atmosphere of dry argon employing i.e., 4-5a-c and 7, and their ruthenium counterparts can be ascribed to the higher activation energies associated to ligand substitution processes in osmium vs. ruthenium complexes, a fact well documented in the literature [16,17,18]
Summary
We recently described the preparation of the ruthenium(II). {η6 :κ1 (P)[RuCl2{η :κ (P)-C6H5(CH2)nOPR2}] (R = Ph, Pr; n = 1, 2, 3; see Scheme 1) starting 2from the i. 1) and starting the from thechloride-bridged corresponding phosphinites corresponding 2)nPh dimers. 6 -arene)} ] (arene = p-cymene, benzene), R2 PO(CH2 )n Ph6-arene)}. ] (arene = p-cymene, benzene), along with their2structural characterization by along with their structural characterization by single-crystal. Single-crystal X-ray diffraction [1]
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