The 2‐(4‐Phenyl‐1H‐1,2,3‐triazol‐1‐yl)ethanol‐Based Phosphinite Ligand Ph2POCH2CH2[1,2,3‐N3C(Ph)C(H)] – Synthesis, Transition‐Metal Complexes, and Structural Studies

Abstract

The synthesis and coordination complexes of the new 1,2,3‐triazole phosphinite Ph2POCH2CH2[1,2,3‐N3C(Ph)C(H)] (2) are described. Compound 2 reacts with H2O2, S8, and Se8 to afford the chalcogenides Ph2P(=E)OCH2CH2[1,2,3‐N3C(Ph)C(H)] [E = O (3), S (4), and Se (5)]. The reaction of 2 with [Ru(η6‐cymene)Cl2] yielded [Ru(η6‐cymene)Cl2(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})] (6), which produced [Ru(η6‐cymene)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})]2[OTf]2 (7) on further treatment with silver triflate (AgOTf); in 7, 2 acts as a bidentate (P,N) ligand. The reaction of 2 with [CpRuCl(PPh3)2] (Cp = cyclopentadienyl) in 1:1 and 1:2 molar ratios afforded the mono‐ and disubstituted complexes [CpRuCl(PPh3)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})] (8) and [CpRuCl(Ph2P‐OCH2CH2{1,2,3‐N3C(Ph)C(H)})2] (9), respectively. Complex 9 reacted with silver triflate to yield the cationic complex [CpRu(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})][OTf] (10), in which one of the phosphinite ligands shows P,N‐chelation. The reactions of 2 with [M(COD)Cl2] (M = Pd, Pt; COD = 1,5‐cyclooctadiene) in 2:1 ratios yielded cis‐[MCl2(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})2] [M = Pd (11) and Pt (12)]. The similar reaction of 2 with [PdCl(η3‐C3H5)]2 in a 2:1 ratio afforded [PdCl(η3‐C3H5)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})] (13). The reaction of 2 with [AuCl(SMe2)] in a 1:1 ratio yielded [Au(Cl)(Ph2POCH2CH2{1,2,3‐N3C(Ph)C(H)})2] (14). The molecular structures of 6, 7, 9, 11, and 12 were determined by single‐crystal X‐ray studies.