文摘
Equimolar and excess ratio reactions of ligands [H{4,5-(P(E)Ph2)2tz}] [tz = 1,2,3-triazole; E = S (1), Se (2)] with Ti(NR2)4 (R = Me, Et) yielded the disubstituted complexes [Ti(NR2)2{κ2-N,E-(4,5-(P(E)Ph2)2tz}2] [E = S, R = Me (3), Et (4); E = Se, R = Me (5), Et (6)], while the reactions of 1 and 2 with Ti(NEt2)2Cl2 gave the monosubstituted complexes [Ti(NEt2)Cl2{κ2-N,E-(4,5-(P(E)Ph2)2tz}] [E = S (7), Se (8)]. The reaction of M(NR2)4 (M = Zr, Hf, R = Me, Et) with 1 and 2 failed. However, the zirconium and hafnium disubstituted complexes, [M(NR2)2{κ2-N,E-(4,5-(P(E)Ph2)2tz}2] [M = Zr, E = S, R = Me (11), Et (12); M = Hf, E = S, R = Me (13), Et (14); M = Zr, E = Se, R = Et (15); M = Hf, E = Se, R = Et (16)] were obtained from the silylated derivatives [SiMe3{κ1-N-(4,5-(P(E)Ph2)2tz}] [E = S(9), Se(10)] and the corresponding metal amides M(NR2)4. In addition, the facile hydrolysis of 5, 7 and 8 with trace amounts of water led to the isolation of compounds 17–19, which contain Ti–O–Ti frameworks.
