Titanium oxo/alkoxo clusters with both phosphonate and methacrylate ligands

Abstract

The clusters Ti5O(OiPr)11(OMc)(O3PR)3 (OMc = methacrylate; R = Et, CH2CH2CH2Br) and Ti10(OiPr)16(OMc)4(O3PCH2CH=CH2)10 were obtained when Ti(OiPr)4 was reacted with the corresponding bis(trimethylsilyl) phosphonate and methacrylic acid. Oxo clusters of the composition Ti6O4(OiPr)10(OMc)2(O3PR)2, with a variety of groups R (Et, Ph, CH=CH2, CH2Ph, CH2CH=CH2, CH2CH2CH2Br, CH2CH2CN, CH2C(O)Me, CH2CH2OC(O)C(Me)=CH2), were formed instead, when a stoichiometric amount of water was added to the reaction mixture.Graphical abstract

Titanium‐Oxo Clusters with Bi‐ and Tridentate Organic Ligands: Gradual Evolution of the Structures from Small to Big

“… R′′=H: R’=C 5 H 4 N, [125] ferrocenyl [140] R′′=Et: R’=Me, [132] CMe=CH 2 [133] R′′=CH=CH 2 , CH 2 CH=CH 2 : R’=Me, [132] CMe=CH 2 [133] R′′=CH 2 ‐naphthyl, CH 2 CH 2 CH 2 Cl, [132] dodecyl: [142] R’=Me R′′=CH 2 CH 2 CH 2 Br, CH 2 CH 2 CN, CH 2 C(O)Me, CH 2 CH 2 OC(O)C(Me)=CH 2 ): R’=CMe=CH 2 [133] R′′=CH 2 Ph: R’=ferrocenyl, [141] CMe=CH 2 [133] R′′=Ph: R’=Me, [143,144] Et, CH 2 Br, CH 2 CN 4 , CH 2 CF 3 , Ph, C 6 H 4 Br, C 6 H 4 Me, C 6 H 4 NO 2 , C 6 F 5 , naphthyl, [144] CMe=CH 2 , [133] O 2 C−C 6 H 4 −COO i Pr, ferrocenyl, [141] C 6 H 4 NMe 2 , C 6 H 4 CN, [145] C 5 H 4 N, [144,146] C 5 H 3 N−NH 2 , [146] C 5 H 3 N−Cl, [139] C 6 H 4 NH 2 , C 6 H 3 (NH 2 ) 2 , C 6 H 4 N=CH−C 6 H 4 NR 2 , C 6 H 3 (N=CH−C 6 H 4 NR 2 ) 2 (R=Et, Ph), [147] C 6 H 4 C(CN)=CH−C 6 H 4 NR 2 (R=Et, Ph), CH 2 CN, [20] dimethylthio‐tetrathiafulvalenyl, 3‐thienyl [19] …”

“…R′′=Ph: R’=Me, [143,144] Et, CH 2 Br, CH 2 CN 4 , CH 2 CF 3 , Ph, C 6 H 4 Br, C 6 H 4 Me, C 6 H 4 NO 2 , C 6 F 5 , naphthyl, [144] CMe=CH 2 , [133] O 2 C−C 6 H 4 −COO i Pr, ferrocenyl, [141] C 6 H 4 NMe 2 , C 6 H 4 CN, [145] C 5 H 4 N, [144,146] C 5 H 3 N−NH 2 , [146] C 5 H 3 N−Cl, [139] C 6 H 4 NH 2 , C 6 H 3 (NH 2 ) 2 , C 6 H 4 N=CH−C 6 H 4 NR 2 , C 6 H 3 (N=CH−C 6 H 4 NR 2 ) 2 (R=Et, Ph), [147] C 6 H 4 C(CN)=CH−C 6 H 4 NR 2 (R=Et, Ph), CH 2 CN, [20] dimethylthio‐tetrathiafulvalenyl, 3‐thienyl [19] …”

“…The construction of Ti 5 O(O i Pr) 11 (O 2 CR’)(O 3 PR′′) 3 (R’=Me, R′′=CH 2 CH 2 CH 2 Br; [132] R’=CMe=CH 2 , R′′=Et, CH 2 CH 2 CH 2 Br; [133] Figure 16 , center left) is based on the same principle as that of Ti 4 O(OR) 8 (O 3 PR′′) 3 L, but the single [TiO 6 ] octahedron is replaced by a pair of edge‐sharing [TiO 6 ] octahedra (3+2 structure). The titanium atoms in the Ti 2 unit are bridged by one μ 2 ‐OR group, one oxygen atom of a R′′PO 3 ligand, and additionally by the carboxylato ligand.…”

Titanium phosphonate oxo-alkoxide “clusters”: solution stability and facile hydrolytic transformation into nano titania

“…37,38 Most titanium phosphonates reported in the literature so far were synthesized under basic conditions (<1 equivalent of phosphonic acid). [39][40][41] In a previous publication we thoroughly investigated the solution stability of two titanium oxo-alkoxides modied with phenylphosphonate ligands using multiple NMR techniques. 42 In this work we synthesized a series of titanium (oxo-) alkoxides modied with tert-butylphosphonic acid, using 0.85, 1, 2 and 4 equivalents of phosphonic acid, to obtain formally basic, neutral and acidic reaction conditions.…”

Synthesis and structural characterization of a dumbbell-like phenylphosphonate-stabilized Ti7–oxide cluster

“…Multidentate phosphonate ligands have a strong coordination ability and multiple coordination sites, which contribute to the formation of higher nuclearity coordination clusters (Pineda et al, 2014;Sheikh et al, 2014;Smith et al, 2014;Packiam & Vidyasagar, 2017). In the course of our research of polyoxotitanium clusters (PTCs) (Liu et al, 2016;Narayanam et al, 2016;Fang et al, 2017;Gao et al, 2017), we noticed that PTCs stabilized by phenylphosphonate ligands are relatively less frequently reported, with some typical examples being from Schubert and co-workers (Czakler et al, 2013(Czakler et al, , 2014(Czakler et al, , 2015. Through a one-step in-situ solvothermal reaction, phenylphosphonate-coordinated [Ti 7 ( 3 -O) 2 (O 3 P-Phen) 6 (O i Pr) 12 ]Á-4H 2 O has been synthesized successfully in high yield.…”