Syntheses and characterizations of trinuclear and dinuclear “half-sandwich” zirconocene phosphates and phosphonates

Abstract

A series of six-coordinate ''half-sandwich'' zirconocene phosphates and phosphonates have been synthesized by the reaction of Cp 2 ZrCl 2 with (diphenyl-, dibenzyl-)phosphate and methylphenylphosphinic acid under different conditions. All of the complexes were characterized by elemental analysis, FT-IR and NMR ( 1 H, 13 C) spectroscopy. Except for complex 3, the structures of complexes 1, 2, 4, 5, and 6 were confirmed by X-ray crystallography. The structure analyses reveal that complexes 1, 2, and 3 are trinuclear complexes with fascinating l 3 -oxygen bridging ligands, central to a Zr-O backbone (Cp 2 ZrCl 2 :ligand is 1:1) while complexes 4, 5, and 6 are centrosymmetric dinuclear complexes built up about the trapezoidal Zr 2 (l 2 -OH) 2 unit (Cp 2 ZrCl 2 :ligand is 1:2).

Molecular Metal Phosphonates

“…73,133,134 All of the known titanium phosphonates are listed in Table 9. 127−137 140 Another interesting alkoxide-bridged dinuclear zirconium phosphinate cage, [(OPr-i) 3 Zr(μ-OPr-i) 2 (μ-OPOPh 2 )Zr-(OPr-i) 2 Ph 2 P(O)(OH)], was obtained in the reaction of [Zr(OPr-i) 4 (i-PrOH)] 2 with Ph 2 P(O)(OH) (Scheme 40). 141 The molecular structure of this compound reveals the presence of a four-membered Zr 2 O 2 core.…”

“…127−137 . 140 The molecular structures of these compounds very closely resemble the O-capped cluster motifs described in the section on tin 95−105 phosphonates and consist of an incomplete cube with four vertices occupied by oxide ions and three by zirconium. Alternate pairs of zirconium centers are bridged by the [R′R″PO 2 ] − ligands.…”

Chromium complexes bearing disubstituted organophosphate ligands and their use in ethylene polymerization

“…The vast majority of the complexes contain phosphate anions with R 0 = R 00 = Me, Et, n Bu, t Bu, Ph or 4-NO 2 -C 6 H 4 groups. Organophosphate complexes with other R 0 and R 00 substituents are still poorly explored (Minyaev et al, 2017(Minyaev et al, , 2018a; there are only 17 structures of such rare-earth metal complexes (Deng et al, 2015;Minyaev et al, 2017Minyaev et al, , 2018aNifant'ev et al, 2013) and 28 structures of transition-metal complexes (Aikawa et al, 2009;Chen et al, 2017a,b;Fortner et al, 2005;Handa et al, 2014;Hrdina et al, 2013;Iwai et al, 2015;Jiang et al, 2011;Lu et al, 2007;Magwaza et al, 2008;McInturff et al, 2012;Minyaev et al, 2018e;Raducan et al, 2012;Rueping & Theissmann, 2010;Wall et al, 1993;Xu et al, 2014;Zhang et al, 2010a).…”

Interplay of thermochemistry and Structural Chemistry, the journal (volume 21, 2010) and the discipline

“…Then experimental paper by Zhang et al [193] follows in which synthesis and characterization by elemental analysis, spectroscopic methods, and X-ray crystal analysis of a series of dinuclear and trinuclear ''half-sandwich''zirconocene complexes derived from (diphenyl-, dibenzyl-)phosphate and methylphenylphosphinic acid is reported. The results reveal the importance of experimental conditions for the design of molecular structures.…”

“…There are but few cases of multiply bridging oxygen for which the thermochemistry is known. Among them are the so called basic beryllium salts or beryllium oxy salts of the generic formula Be 4 OX 6 with a l 4 -oxygen at its core (X = nitrate [194], acetate [195], and propionate [193]). …”