Group 4 complexes supported by nitrogen-rich heterocycles bearing chalcogen donor atoms. (28th May 2016)

• Record Type: Journal Article
• Authors: Bernabé-Pablo, Erandi; Campirán-Martínez, Azucena; Jancik, Vojtech; Martínez-Otero, Diego; Moya-Cabrera, Mónica
• Is Part Of: Polyhedron. Volume 110(2016)
• Page Start: 305
• Page End: 313
• Publication Date: 2016-05-28
• Subjects: Chalcogen -- 1, 2, 3-Triazole -- Group 4 metals -- X-ray structure -- Phosphorus; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2015.08.004
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Disubstituted group 4 complexes bearing triazole based chalcogen ligands were prepared by acid–base reactions. The selective formation of the symmetric N, N isomers is observed in the solid state while in solution a fluxional behavior is present. Hydrolysis of mono- and disubstituted titanium complexes led to compounds with Ti–O–Ti frameworks. Abstract: Equimolar and excess ratio reactions of ligands [H{4, 5-(P(E)Ph2 )2 tz}] [tz = 1, 2, 3-triazole; E = S (1 ), Se (2 )] with Ti(NR2 )4 (R = Me, Et) yielded the disubstituted complexes [Ti(NR2 )2 {κ 2 - N, E -(4, 5-(P(E)Ph2 )2 tz}2 ] [E = S, R = Me (3 ), Et (4 ); E = Se, R = Me (5 ), Et (6 )], while the reactions of1 and2 with Ti(NEt2 )2 Cl2 gave the monosubstituted complexes [Ti(NEt2 )Cl2 {κ 2 - N, E -(4, 5-(P(E)Ph2 )2 tz}] [E = S (7 ), Se (8 )]. The reaction of M(NR2 )4 (M = Zr, Hf, R = Me, Et) with1 and2 failed. However, the zirconium and hafnium disubstituted complexes, [M(NR2 )2 {κ 2 - N, E -(4, 5-(P(E)Ph2 )2 tz}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 {κ 1 - N -(4, 5-(P(E)Ph2 )2 tz}] [E = S(9 ), Se(10 )] and the corresponding metal amides M(NR2 )4 . In addition, the facile hydrolysis of5, 7 and8 with trace amounts of water led to the isolation of compounds17 –19, which contain Ti–O–Ti frameworks.