The synthesis of W–O–M (M=Al, Ti, Ni, Zn) μ–oxo clusters by hydrolysis of tungsten aminoalkoxides and their structural characterisation

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[120] Two structurally related oxo clusters of tungsten, [(W(O)(tdmap)}4O6] (180, tdmap = OC(CH2NMe2)3) and [{(W(O)(S-Phoz)}4O6] (181, S-Phoz = 2-(4',4'-dimethyloxazoline-2'-yl)thiophenolate), are known in the literature. [121,122] The first from a reaction of [W(O)(O i Pr)4] with Htdmap in the presence of water and the second by rearrangement of the complex [W(CO)(C2Me2)(S-Phoz)2] after oxidation using pyridine-Noxide. One sulfide containing adamantane-type cluster [(WPMe2Ph)4S6] (182) exists, which rearranges from the tetranuclear [W4(μ3-S)2(μ-S)4Cl2(PMe2Ph)6] after reduction with a Na/Hg amalgam in low yields.…”

“…A mixed W/Ti oxygen adamantane-type structure [(W(O)O i Pr)2{Ti(O i Pr)2}2(O)4(bdmap)2] (910, Hbdmap = 1,3-bis-(dimethylamino)-propan-2-ol) was obtained after a reaction of the complex [W(O)(O i Pr)3(bdmap)] with Hbdmap and Ti(O i Pr)4, followed by a hydrolysis in a H2O / i PrOH mixture. [122] There are also examples of mixed adamantanes accessible directly from the elements and simple binary compounds if the correct additives and conditions are used.…”

“…[µ4-O{(thf)Cl2Zr}4(OMe)6], AlMe3 / THF, PhMe, 12 h R [512] J [174] [(µ3-Cu){Cu(PEt3)3}3(GaMe)(SePh)3(μ3-SePh)3] (908) [(PEt3)5(CuSePh)6], Me3SiSePh, [Me2GaSePh]n / THF J [174] [(µ3-Cu){Cu(PEt3)3}3(GaMe)(TePh)3(μ3-TePh)3] (909) [(PEt3)5(CuTePh)6], Me3SiTePh, Me3Ga•OEt2 / THF J [174] [(W(O)O i Pr)2{Ti(O i Pr)2}2(O)4(bdmap)2] (910) [W(O)(O i Pr)3(bdmap)], Hbdmap, Ti(O i Pr)4 / PhMe, H2O, HO i Pr, 2 days, 110 °C to 0 °C C/I [122] [H3TAEA]2[InGe4S11(SH)2(OH)] ( 911) In(NO3), GeO2, TAEA / (CH2OH)2, n BuNH2, (CH2SH)2, 170 °C, 5 days B [518] [{Ni(bme*daco)}2(CuCl)4] (912) (bme*daco)Ni, CuCl / MeCN K [489] Hbdmap = 1,3-bis-(dimethylamino)-propan-2-ol, n Hep = normal heptane, TAEA = tris(2-aminoethyl)amine…”

“…120 Two structurally related oxo clusters of tungsten, [(W(O)(tdmap)} 4 O 6 ] (180, tdmap = OC(CH2NMe 2 ) 3 ) and [{(W(O)(S-Phoz)} 4 O 6 ] (181, S-Phoz = 2-(4 0 ,4 0 -dimethyloxazoline-2 0 -yl)thiophenolate), are known in the literature. 121,122 The rst from a reaction of [W(O)(O i Pr) 4 ] with Htdmap in the presence of water and the second by rearrangement of the complex [W(CO)(C 2 Me 2 )(S-Phoz) 2 ] aer oxidation using pyridine-Noxide.…”

“…) 6 ] (906-909, E = Se, R = Me, Et, Et 2 i Pr; E = Te, R = Et) 174. They are obtained aer reacting the complexes [(PR 3 ) 5 (CuEPh) 6 ] with chalcogenidolates and a GaMe source.A mixed W/Ti oxygen adamantane-type structure [(W(O) O i Pr) 2 {Ti(O i Pr) 2 } 2 (O) 4 (bdmap) 2 ] (910, Hbdmap = 1,3-bis-(dimethylamino)-propan-2-ol) was obtained aer a reaction of the complex [W(O)(O i Pr) 3 (bdmap)] with Hbdmap and Ti(O i Pr) 4 , followed by a hydrolysis in a H 2 O/ i PrOH mixture 122. …”