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

The synthesis and coordination complexes of the new 1,2,3‐triazole phosphinite Ph 2 POCH 2 CH 2 [1,2,3‐N 3 C(Ph)C(H)] ( 2 ) are described. Compound 2 reacts with H 2 O 2 , S 8 , and Se 8 to afford the chalcogenides Ph 2 P(=E)OCH 2 CH 2 [1,2,3‐N 3 C(Ph)C(H)] [E = O ( 3 ), S ( 4 ), and Se ( 5 )]. The reaction of 2 with [Ru(η 6 ‐cymene)Cl 2 ] yielded [Ru(η 6 ‐cymene)Cl 2 (Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)})] ( 6 ), which produced [Ru(η 6 ‐cymene)(Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(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(PPh 3 ) 2 ] (Cp = cyclopentadienyl) in 1:1 and 1:2 molar ratios afforded the mono‐ and disubstituted complexes [CpRuCl(PPh 3 )(Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)})] ( 8 ) and [CpRuCl(Ph 2 P‐OCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)}) 2 ] ( 9 ), respectively. Complex 9 reacted with silver triflate to yield the cationic complex [CpRu(Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)})(Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)})][OTf] ( 10 ), in which one of the phosphinite ligands shows P,N‐chelation. The reactions of 2 with [M(COD)Cl 2 ] (M = Pd, Pt; COD = 1,5‐cyclooctadiene) in 2:1 ratios yielded cis ‐[MCl 2 (Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)}) 2 ] [M = Pd ( 11 ) and Pt ( 12 )]. The similar reaction of 2 with [PdCl(η 3 ‐C 3 H 5 )] 2 in a 2:1 ratio afforded [PdCl(η 3 ‐C 3 H 5 )(Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)})] ( 13 ). The reaction of 2 with [AuCl(SMe 2 )] in a 1:1 ratio yielded [Au(Cl)(Ph 2 POCH 2 CH 2 {1,2,3‐N 3 C(Ph)C(H)}) 2 ] ( 14 ). The molecular structures of 6 , 7 , 9 , 11 , and 12 were determined by single‐crystal X‐ray studies.