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Phosphole and azaphosphole derivatives with triazole functionalities, [C 6 H 5 {1,2,3-N 3 CC 6 H 4 C(PPh)}] (L1) and [C 6 H 4 {1,2,3-N 3 C(Ph)C(PPh)}] (L2) were synthesized by reacting [(C 6 H 5 )(1,2,3-N 3 C = CH- o -Br-C 6 H 4 )] and [( o -Br-C 6 H 4 )(1,2,3-N 3 C = CHC 6 H 5 )] with n BuLi followed by the addition of dichlorophenylphosphine. The reactions of L1 and L2 with an excess of 30% H 2 O 2 afforded phosphole oxides [C 6 H 5 {1,2,3-N 3 CC 6 H 4 C(P(O)Ph)}] (L1O) and [C 6 H 4 {1,2,3-N 3 C(Ph)C(P(O)Ph)}] (L2O) as white crystalline solids. Stoichiometric reactions of L1 and L2 with [Ru(η 6 - p -cymene)Cl 2 ] 2 in CH 2 Cl 2 yielded [RuCl 2 (η 6 - p -cymene)(L1-κ 1 - P )] (1) and [RuCl 2 (η 6 - p -cymene)(L2-κ 1 - P )] (2), respectively. Similar reactions of L1 and L2 with [Pd(COD)Cl 2 ] and [Pd(η 3 -C 3 H 5 )Cl] 2 produced the corresponding complexes, trans -[PdCl 2 (L1-κ 1 - P ) 2 ] (3), trans -[PdCl 2 (L2-κ 1 - P ) 2 ] (4), [Pd(η 3 -C 3 H 5 )Cl(L1-κ 1 - P )] (5), and [Pd(η 3 -C 3 H 5 )Cl(L2-κ 1 - P )] (6). Treatment of L1 with [AuCl(SMe 2 )] in dichloromethane afforded [AuCl(L1-κ 1 - P )] (7). Ruthenium complex 1 showed moderate to good catalytic activity towards benzylic C-H oxidation, and the proposed mechanism for the catalysis was supported by spectroscopic data.