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

The crystal structures of three unusual chromium organophosphate complexes have been determined, namely, bis(μ-butyl 2,6-di-tert-butyl-4-methylphenyl hydrogen phosphato-κO:κO')di-μ-hydroxido-bis[(butyl 2,6-di-tert-butyl-4-methylphenyl hydrogen phosphato-κO)(butyl 2,6-di-tert-butyl-4-methylphenyl phosphato-κO)chromium](Cr-Cr) heptane disolvate or {Cr(μ-OH)[μ-PO(OBu)(O-2,6-Bu-4-MeCH)-κO:κO'][PO(OBu)(O-2,6-Bu-4-MeCH)-κO][HOPO(OBu)(O-2,6-Bu-4-MeCH)-κO]}·2CH, [Cr(CHOP)(CHOP)(OH)]·2CH, denoted (1)·2(heptane), [μ-bis(2,6-diisopropylphenyl) phosphato-1κO:2κO']bis[bis(2,6-diisopropylphenyl) phosphato]-1κO,2κO-chlorido-2κCl-triethanol-1κO,2κO-di-μ-ethanolato-1κO:2κO-dichromium(Cr-Cr) ethanol monosolvate or {Cr(μ-OEt)[μ-PO(O-2,6-Pr-CH)-κO:κO'][PO(O-2,6-Pr-CH)-κO]Cl(EtOH)}·EtOH, [Cr(CHO)(CHOP)Cl(CHO)]·CHO, denoted (2)·EtOH, and di-μ-ethanolato-1κO:2κO-bis{[bis(2,6-diisopropylphenyl) hydrogen phosphato-κO][bis(2,6-diisopropylphenyl) phosphato-κO]chlorido(ethanol-κO)chromium}(Cr-Cr) benzene disolvate or {Cr(μ-OEt)[PO(O-2,6-Pr-CH)-κO][HOPO(O-2,6-Pr-CH)-κO]Cl(EtOH)}·2CH, [Cr(CHO)(CHOP)(CHOP)Cl(CHO)]·2CH, denoted (3)·2CH. Complexes (1)-(3) have been synthesized by an exchange reaction between the in-situ-generated corresponding lithium or potassium disubstituted phosphates with CrCl(HO) in ethanol. The subsequent crystallization of (1) from heptane, (2) from ethanol and (3) from an ethanol/benzene mixture allowed us to obtain crystals of (1)·2(heptane), (2)·EtOH and (3)·2CH, whose structures have the monoclinic P2, orthorhombic P222 and triclinic P-1 space groups, respectively.

[Bis(2,6-diiso-propyl-phen-yl) phosphato-κ]pentakis-(methanol-κ)manganese bis-(2,6-diiso-propyl-phen-yl) phosphate methanol tris-olvate.

The title compound, [Mn(CHOP)(CHOH)](CHOP)·3CHOH, was formed in the reaction between a hydrate of a manganese(II) salt [either Mn(NO)(HO) or MnCl(HO)] with a methanol solvate of lithium bis-(2,6-diiso-propyl-phen-yl) phosphate, {Li[OOP(O-2,6- PrCH)]·(CHO)}·CHO, in methanol. The structure has monoclinic () symmetry at 150 K. The complex consists of an [Mn{OOP(O-2,6- PrCH)}(CHOH)] cation, an [OOP(O-2,6- PrCH)] anion and three non-coordinating methanol mol-ecules.

Dinuclear neodymium and lanthanum bis(2,6-diisopropylphenyl) phosphate complexes bearing a hydroxide ligand: catalytic activity of the Nd complex in 1,3-diene polymerization.

The reactions of K[(2,6-PrCH-O)POO] either with LaCl(HO) or with Nd(NO)(HO) in a 3:1 molar ratio, followed by vacuum drying and recrystallization from alkanes, have led to the formation of diaquapentakis[bis(2,6-diisopropylphenyl) phosphato]-μ-hydroxido-dilanthanum hexane disolvate, [La(CHOP)(OH)(HO)]·2CH, (1)·2(hexane), and tetraaquatetrakis[bis(2,6-diisopropylphenyl) phosphato]-μ-hydroxido-dineodymium bis(2,6-diisopropylphenyl) phosphate heptane disolvate, [Nd(CHOP)(OH)(HO)]·2CH, (2)·2(heptane). The compounds crystalize in the P2/n and P-1 space groups, respectively. The diaryl-substituted organophosphate ligand exhibits three different coordination modes, viz.

Crystal structure and catalytic activity of tetra-kis-(μ-ethyl 2,6-di--butyl-4-methyl-phenyl phos-phato-κ:')bis-(ethyl 2,6-di--butyl-4-methyl-phenyl phosphato-κ,')dilutetium -heptane disolvate.

The title complex, [Lu(CHOP)]·2CH, was formed in the reaction between potassium 2,6-di--butyl-4-methyl-phenyl ethyl phosphate, [K(2,6- Bu-4-MeCH-O)(EtO)PO], and LuCl(HO) in water, followed by vacuum drying and recrystallization from heptane. Its crystal structure has triclinic ( [Formula: see text]) symmetry at 120 K. The lutetium tris-(phosphate) complex has a binuclear [Lu(μ-OPO)] core and the organophosphate ligand exhibits κ,' terminal and μ-κ:κ' bridging coordination modes with the Lu ion being sixfold coordinated.

Isomorphous rare-earth tris[bis(2,6-diisopropylphenyl) phosphate] complexes and their catalytic properties in 1,3-diene polymerization and in the inhibited oxidation of polydimethylsiloxane.

Crystals of mononuclear tris[bis(2,6-diisopropylphenyl) phosphato-κO]pentakis(methanol-κO)lanthanide methanol monosolvates of lanthanum, [La(CHOP)(CHOH)]·CHOH, (1), cerium, [Ce(CHOP)(CHOH)]·CHOH, (2), and neodymium, [Nd(CHOP)(CHOH)]·CHOH, (3), have been obtained by reactions between LnCl(HO) (n = 6 or 7) and lithium bis(2,6-diisopropylphenyl) phosphate in a 1:3 molar ratio in methanol media. Compounds (1)-(3) crystallize in the monoclinic P2/c space group and have isomorphous crystal structures. All three bis(2,6-diisopropylphenyl) phosphate ligands display a κO-monodentate coordination mode.

Isomorphous rare-earth bis[bis(2,6-diisopropylphenyl)phosphate] complexes and their self-assembly into two-dimensional frameworks by intramolecular hydrogen bonds.

The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]chloridotetrakis(methanol-κO)neodymium methanol disolvate, [Nd(CHOP)Cl(CHO)]·2CHOH, (1), and of the lutetium, [Lu(CHOP)Cl(CHO)]·2CHOH, (2), and yttrium, [Y(CHOP)Cl(CHO)]·2CHOH, (3), analogues have been obtained by reactions between lithium bis(2,6-diisopropylphenyl)phosphate and LnCl(HO) (in a 2:1 ratio) in methanol. Compounds (1)-(3) crystallize in the C2/c space group.

Crystal structure of [bis-(2,6-diiso-propyl-phen-yl) phosphato-κO]tris-(methanol-κO)lithium methanol monosolvate.

Crystals of the title compound, [Li{OOP(O-2,6-(i)Pr2C6H3)2}(CH3OH)3]·CH3OH or [Li(C24H34O4P)(CH3OH)3]·CH3OH, have been formed in the reaction between HOOP(O-2,6-(i)Pr2C6H3)2 and LiOH in methanol. The title compound is of inter-est as it represents the first reported crystal structure of the family of lithium phosphate diesters. The {Li(CH3OH)3[O2P(O-(i)Pr2C6H3)2]} unit displays the Li atom in a slightly distorted tetra-hedral coordination environment and exhibits one intra-molecular O-H⋯O hydrogen bond between a coordinating methanol mol-ecule and the terminal non-coordinating O atom of the phosphate group.

Easily accessible, hydrocarbon-soluble, crystalline, anhydrous lanthanide (Nd, La, and Y) phosphates.

Nd, La and Y triphosphates were prepared via the reaction of potassium ionol ethyl phosphate with the corresponding lanthanide nitrates or chlorides in water. According to the X-ray diffraction data, the recrystallised reaction products were dimers. The products did not contain water, were readily soluble in hydrocarbon solvents and demonstrated promising catalytic properties in the polymerisation of butadiene and DL-dilactide.