Thioether macrocyclic chemistry: Synthesis of [RhCl([15]aneS 5)] 2+ and [Ru(PPh 3)([15]aneS 5)] 2+. The single crystal X-ray structure of [Ru(PPh 3)([15]aneS 5)](BPh 4) 2 ([15]aneS 5 = 1,4,7,10,13-pentathiacyclopentadecane)

Abstract

Reaction of RhCl 3 with one molar equivalent of [15]aneS 5 in refluxing MeOH yields a yellow solution containing the complex cation [RhCl([15]aneS 5)] 2+. Addition of excess NH 4PF 6 affords the complex [RhCl([15]aneS 5)](PF 6) 2 as a yellow solid, which can be recrystallized from MeCN. [RhCl([15]aneS 5)] 2+ shows two irreversible reductions at E pc = −0.78 and −1.93 V vs Fc/Fc + at a scan rate of 200 mV s −1. Treatment of [RuCl 2(PPh 3) 3] with one molar equivalent of [15]aneS 5 in refluxing MeOH, followed by addition of excess NH 4PF 6 or NaBPh 4 affords [Ru(PPh 3)([15]aneS 5)]X 2 (X = PF 6 − or BPh 4 −) as a yellow solid, which can be recrystallized from MeCN/diethyl ether. [Ru(PPh 3) ([15]aneS 5)](BPh 4) 2 has been characterized by X-ray crystallography. The structure confirms coordination of all five macrocyclic thioether donors, RuS(1) = 2.3371(15), RuS(4) = 2.3785(12), RuS(7) = 2.4458(10), RuS(10) = 2.3732(15), RuS(13) = 2.3099(10) Å, and the P donor of the PPh 3 ligand, RuP = 2.3679(8) Å, to give an overall distorted octahedral stereochemistry at ruthenium(II).