Biphenoxo complexes of tungsten(VI), [WCl 4 {CHR[C 6 H 2 (Bu t ) 2 O] 2 }] R=H (1), Me (2) are reduced by Na/Hg in the presence of PMe 3 to give cis, trans-WCl 2 (PMe 3 ) 2 {CHR[C 6 H 2 (Bu t ) 2 O] 2 } R=H (3), Me (4). Reaction of [WOCl 4 ] with the biphenols 2,2′-CHR[C 6 H 2 (Bu t ) 2 OH] 2 in diethyl ether gives [WOCl 2 {CHR[C 6 H 2 (Bu t ) 2 O] 2 }] R=H (5), Me (6). Similar treatment of [W(NPh)Cl 4 (Et 2 O)] gives the complex [W(NPh)Cl 3 {(1,1′-O,OH)(2,2′-CH 3 CH)[4,6-(Bu t ) 2 C 6 H 2 ] 2 }] (7) containing the monoanionic ligand {(1,1′-O,OH)(2,2′-CH 3 CH)[4,6-(Bu t ) 2 C 6 H 2 ] 2 } − . Reaction of [WOCl 4 ] with the linear triphenol 2,6-bis(3,5-di-t-butyl-2-hydroxybenzyl)-4-methylphenol, HOArCH 2 Ar 1 (OH)CH 2 ArOH (Ar=4,6-di-t-butylphenol; Ar 1 =4-methylphenyl), in refluxing toluene affords the centrosymmetric complex {WOCl[OArCH 2 Ar 1 (O)CH 2 ArO]} 2 (8), in which the mer-tridentate ligands adopt the U-conformation. The related complex {WOCl[OAr 2 CH 2 Ar 3 (O)CH 2 Ar 2 O]} (9) has been isolated as a hydrolysis product from the reaction of [W(NPh)Cl 4 (Et 2 O)] and 2,6-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-t-butylphenol, HOAr 2 CH 2 Ar 3 (OH)CH 2 Ar 2 OH (Ar 2 =4-methyl-6-t-butylphenol; Ar 3 =4-t-butylphenyl), and is also available via [WOCl 4 ]. Reaction of [W(eg) 3 ] (eg=1,2-ethanediolato) with 2,6-bis(3,5-methyl-2-hydroxybenzyl)-4-t-butylphenol, HOAr 4 CH 2 Ar 3 (OH)CH 2 Ar 4 OH(Ar 4 =4,6-di-methylphenol) affords [W(eg) 2 (OAr 4 CH 2 Ar 3 (O)CH 2 Ar 4 OH)] (10), containing a chelating biphenolate ligand with a pendant phenolic group. Crystal structures of complexes 1, 3, 5, 8, 9 and 10 are reported.