Bismuth and Titanium Phosphinates: Isolation of Tetra-, Hexa- and Octanuclear Clusters

Abstract

The reaction of organobismuth precursors with trityl-H-phosphinic acid in varying reaction conditions afforded colorless crystals, whose single crystal X-ray characterization revealed the formation of monomerThe reaction of titanium isopropoxide with two different phosphinic acids trityl-H-phosphinic acid and cycP(O)(OH) led to isolation of cubane type octahedral complex {Ti 8 (μ 2 -O) 8 (μ 2 -OH) 4 [(Ph 3 C)(H)PO 2 ] 12 }[3C 7 H 8 ] (3) and hexanuclear complex Ti 6 (μ 2 -cycPO 2 ) 9 (μ 2 -O) 6 (μ 2 -OH) 3 •4CH 3 CN•4H 2 O (4) respectively.

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

“…The construction principle of corner‐sharing polyhedra was also found for Ti 8 O 8 (OH) 4 [O 2 P(H)CPh 3 ] 12 , [107] with a cubic arrangement of eight [TiO 6 ] octahedra (= two rings of four [TiO 6 ] octahedra), each edge of the cube being bridged by a phosphinato ligand.…”

“…However, a ring of only six corner‐sharing [TiO 6 ] octahedra was found with phosphinato instead of carboxylato ligands. Two neighboring titanium atoms in Ti 6 O 6 (OH) 3 (O 2 P‐ cyclo ‐C 3 Me 5 ) 9 are alternatively bridged by two pentamethyltrimethylene phosphinato ligands and one μ 2 ‐OH, or one phosphinato ligand and two μ 2 ‐O [107] . Bridging phosphinato ligands are more flexible than carboxylato ligands and can therefore possibly adjust easier to varying Ti−Ti distances.…”

“…Two neighboring titanium atoms in Ti 6 O 6 (OH) 3 (O 2 P‐ cyclo ‐C 3 Me 5 ) 9 are alternatively bridged by two pentamethyltrimethylene phosphinato ligands and one μ 2 ‐OH, or one phosphinato ligand and two μ 2 ‐O. [107] Bridging phosphinato ligands are more flexible than carboxylato ligands and can therefore possibly adjust easier to varying Ti−Ti distances. Rings of only four corner‐sharing [TiO 6− x N x ] octahedra were observed in [Ti 4 O 4 (C 2 O 4 ) 8 ] 8− and [Ti 4 O 4 (nitrilotriacetato) 4 ] 4− (see above).…”

Aryl bismuth phosphinates [BiAr2(O(O)PRR′)]: structure–activity relationships for antibacterial activity and cytotoxicity

“…The complexes adopt a 1D coordination polymer with bridging phosphinato groups connecting the bismuth atom, as similarly found for the previously reported di-phenyl bismuth mono-phosphinato complexes, as well as transition metal and other group 15 complexes. 27,[33][34][35][36][37][38][39][40] Attempts to crystallise the remaining complexes from DMSO proved unsuccessful, especially in the case of the o-methoxyphenyl bismuth…”

In Situ Assembled Polynuclear Zinc Oxo Clusters Using Modified Schiff Bases as Ligands

“… 4 We have recently shown the assembly of titanium-based multinuclear clusters, one of which shows interesting structural properties such as fluxional behavior at room temperature. 5 Moreover, we have also recently shown a designed approach for reducing band gaps by synthesizing Ti 4 Sb 2 -based heteronuclear clusters from a parent Sb 6 molecular framework using solvothermal reaction conditions. 6 We have also been using multidentate donating ligands such as Schiff-base ligands due to their adjustable coordination properties and flexible bridging modes.…”