Hetero-tri-spin 2p-3d-4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo-Ligands: Synthesis, Structure, and Magnetic Properties

Employing nitronyl nitroxide lanthanide(III) complexes as metallo-ligands allowed the efficient and highly selective preparation of three series of unprecedented heterotri-spin (Cu Ln-radical) one-dimensional compounds. These 2p-3d-4f spin systems, namely Ln(3)Cu(hfac)II(NitPhOAII)41 (Ln(III)=Gd 1(Gd), Tb 1(Tb), Dy 1(Dy); NitPhOAII=2-(4'-allyloxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3- oxide), Ln(3)Cu(hfac)II(NitPhOPO4] (1-nrn=Gd 2Gd, Tb 2Tb, Dy 2(Dy), Ho 2HOf Yb 2yb; NitPhOPr= 2-(4'-propoxyphenyI)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) and Ln3Cu(hfac)II(NitPhOB441 (LnIm=Gd 3Gd, Tb 3Tb, Dy 3(Dy); NitPhOBz=2-(4'-benzyloxy- phenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) involve O-bound nitronyl nitroxide radicals as bridging ligands in chain structures with a Cu-Nit-Ln-Nit-Ln-Nit-Ln-Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal radical interactions take place in these heterotri-spin chain complexes, these and the next-neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single-chain magnet behavior.

Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide Catalyzed by Noncyclopentadienyl Rare-Earth Metal Bis(alkyl) Complexes

The syntheses of several dialkyl complexes based on rare-earth metal were described. Three beta-diimine compounds with varying N-aryl substituents (HL1 = (2-CH3O(C6H4))N=C(CH3)CH=C(CH3)NH(2-CH3O(C6H4)), HL2 = (2,4,6-(CH3)(3) (C6H2))N=C(CH3)CH=C(CH3)NH(2,4,6-(CH3)(3)(C6H2)), HL3 = PhN=C(CH3)CH(CH3) NHPh) were treated with Ln(CH2SiMe3)(3)(THF)(2) to give dialkyl complexes L(1)Ln (CH2SiMe3)(2) (Ln = Y (1a), Lu (1b), Sc (1c)), L(2)Ln(CH2SiMe3)(2)(THF) (Ln = Y (2a), Lu (2b)), and (LLu)-Lu-3(CH2SiMe3)(2)(THF) (3). All these complexes were applied to the copolymerization of cyclohexene oxide (CHO) and carbon dioxide as single-component catalysts.

Thiophene-NPN Ligand Supported Rare-Earth Metal Bis(alkyl) Complexes. Synthesis and Catalysis toward Highly trans-1,4 Selective Polymerization of Butadiene

A series of new rare-earth metal bis(alkyl) complexes [L(1-3)Ln(CH2SiMe3)(2)(THF)(n)] (L-1 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H2Me3-2,4,6: Ln = Sc, n = 1 (1a); Ln = Lu, n = 1 (1b); L-2 = MeC4H2SCH2NC6H4(Ph)(2)P=NC6H3Et2-2,6: Ln = Sc, n = 1 (2a); Ln = Lu, n = 1 (2b); Ln = Y, n = 1 (2c); L-3 = MeC4H2SCH2NC6H4(Ph)(2)P=(NC6H3Pr2)-Pr-i-2,6: Ln = Sc, n = 0 (3a)) and (LSc)-Sc-4(CH2SiMe3)(2()THF) (4a) (L-4 = C6H5CH2NC6H4(Ph)(2)P=NC6H3Et2-2,6) have been prepared by reaction of rare-earth metal tris(alkyl)s with the corresponding HL1-4 ligands via alkane elimination.

Lanthanide-hinged calixarene bicapsules: Discrete hexanuclear Ln(III)/phenanthroline/p-sulfonatocalix[4]arene oligomers (Ln = Gd, Tb)

The dumbbell-like calixarene bicapsule in two novel Ln(III)-C4AS compounds was found to be a hexanuclear Ln(III)/phenanthroline/p-sulfonatocalix[4]arene oligomer. The magnetic and luminescent properties of these compounds were examined.

Reactivity of Rare-Earth Metal Complexes Stabilized by an Anilido-Phosphinimine Ligand

Treatment of anilido-phosphinimine-ligated yttrium mono(alkyl) complex 1a, LY(CH2Si(CH3)(3))(THF) (L = o-(2,6-(C6H3Pr2)-Pr-i)NC6H4P(C6H4)(C6H5)N(2,4,6-C6H2Me3)), with 2 equiv of phenylsilane in DME afforded methoxy-bridged complex 2, [LY(mu-OCH3)](2), via the corresponding hydrido intermediate. When excess isoprene was added to the mixture of la and phenylsilane, a eta(3)-isopentene product, 3, LY(CH2C(CH3)=CHCH3)(THF), was isolated. A lutetium chloride, LLuCl(DME) (4), was generated through the reaction of lutetium mono(alkyl) complex 1b, LLu(CH2Si(CH3)(3))(THF), with [Ph3C]-[B(C6F5)(4)]center dot LiCl accompanied by the formation of [Li(DME)(3)](+)[B(C6F5)(4)](-). Metathesis reaction of 1b with excess AlMe3 at room temperature gave a methyl-terminated counterpart, 5, LLu(CH3)(THF)(2). In all these reactions, the Ln-C-phenyl bonds of complexes 1 remained untouched.

Copolymerization of ethylene with norbornene catalyzed by cationic rare earth metal fluorenyl functionalized N-heterocyclic carbene complexes

Rare earth metal bis(alkyl) complexes attached by fluorenyl modified N-heterocyclic carbene (NHC) (Flu-NHC)Ln(CH2SiMe3)(2) (Flu-NHC = (C13H8CH2CH2(NCHCCHN)C6H2Me3-2,4,6); Ln = Sc (2a); Y (2b); Ho (2c); Lu (2d)), ((tBu)Flu-NHC)Ln(CH2SiMe3)(2) ((tBu)Flu-NHC = 2,7-(Bu2C13H6CH2CH2)-Bu-t(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (1a); Lu (1d)) and attached by indenyl modified N-heterocyclic carbene (Ind-NHC)Ln(CH2SiMe3)(2) (Ind-NHC = C9H6CH2CH2(NCHCCHN)C6H2Me3-2,4,6; Ln = Sc (3a); Lu (3d)), under the activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)(4)], showed varied catalytic activities toward homo- and copolymerization of ethylene and norbornene. Among which the scandium complexes, in spite of ligand type, exhibited medium to high catalytic activity for ethylene polymerization (10(5) g mol(Sc)(-1) h(-1) atm(-1)), but all were almost inert to norbornene polymerization. Remarkably, higher activity was found for the copolymerization of ethylene and norbornene when using Sc based catalytic systems, which reached up to 5 x 10(6) g mol(Sc)(-1) h(-1) atm(-1) with 2a. The composition of the isolated copolymer was varying from random to alternating according to the feed ratio of the two monomers (r(E) = 4.1, r(NB) = 0.013).

Organolanthanides with 3-(2-pyridylmethyl) indenyl ligands: synthesis, crystal structures and catalytic activities of divalent complexes for epsilon-caprolactone polymerization

Reaction of 3-(2-pyridylmethyl)indenyl lithium (1) with LnI(2)(THF)(2) (Ln = Sm, Yb) in THF produced the divalent organolanthanides (C5H4NCH2C9H6)(2)Ln(II)(THF) (Ln = Sm (2), Yb (3)) in high yield. 1 reacts with LnCl(3) (Ln = Nd, Sm, Yb) in THF to give bis(3-(2-pyridylmethyl)indenyl) lanthanide chlorides (C5H4NCH2C9H6)(2)Ln(III)Cl (Ln = Nd (4), Sm (5)) and the unexpected divalent lanthanides 3 (Ln = Yb). Complexes 2-5 show more stable in air than the non-functionalized analogues. X-ray structural analyses of 2-4 were performed. 2 and 3 belong to the high symmetrical space group (Cmcm) with the same structures, they are THF-solvated 9-coordinate monomeric in the solid state, while 4 is an unsolvated 9-coordinate monomer with a trans arrangement of both the side-arms and indenyl rings in the solid state. Additionally, 2 and 3 show moderate polymerization activities for F-caprolactone (CL).

Synthesis and structural characterization of beta-diketiminate-lanthanide Amides and their catalytic activity for the polymerization of methyl methacrylate and epsilon-caprolactone

The synthesis and catalytic activity of lanthanide monoamido complexes supported by a beta-diketiminate ligand are described. Donor solvents, such as DME, can cleave the chloro bridges of the dinuclear beta-diketiminate ytterbium dichloride {[(DIPPh)(2)nacnac]YbCl(mu-Cl)(3)Yb[(DIPPh)(2)nacnac](THF)} (1) [(DIPPh)(2)nacnac = N,N-diisopropylphenyl-2,4-pentanediimine anion] to produce the monomeric complex [(DIPPh)(2)nacnac]YbCl2(DME) (2) in high isolated yield. Complex 2 is a useful precursor for the synthesis of beta-diketiminate-ytterbium monoamido derivatives. Reaction of complex 2 with 1 equiv of LiNPr2i in THF at room temperature, after crystallization in THF/toluene mixed solvent, gave the anionic beta-diketiminate-ytterbium amido complex [(DIPPh)(2)nacnac]Yb(NPr2i)(mu-Cl)(2)Li(THF)(2) (3), while similar reaction of complex 2 with LiNPh2 produced the neutral complex [(DIPPh)(2)nacnac]Yb(NPh2)Cl(THF) (4). Recrystallization of complex 3 from toluene solution at elevated temperature led to the neutral beta-diketiminate-lanthanide amido complex [{(DIPPh)(2)nacnac}Yb(NPr2i)(mu-Cl)](2) (5). The reaction medium has a significant effect on the outcome of the reaction.

Synthesis and crystal structure of bis(tetrahydrofurfurylindenyl) lanthanide chlorides

Lanthanocene chlorides (C4H7OCH2C9H6)(2)LnCl[Ln=Y(1); Ln=Gd(2)] were synthesized by the reaction of tetrahydrofurfurylindenyl lithium(in situ) with corresponding anhydrous lanthanide chorides in THF. The crystal structures of these two complexes were determined by X-ray diffraction and they were unsolvated monomeric complexes. They were stable in the air for several hours. Complexes 1 and 2 belong to the same crystal system (orthorhombic) and space group(P2(1)2(1)2(1)). The unit cell dimensions of complex 1 were a=1.042 52(9) nm, b=1.47455(12) nm, c=1.497 99(13) nm, Z=4, D-c=1.508 g/cm(3); The unit cell dimensions of complex 2 were a=1.037 01(10) nm, b=1.472 33(12) nm, c=1.513 54(14) nm, Z=4, D-c=1.699 g/cm(3). They have the same structure and different space configurations. The central metal atom is coordinated by two indenyl, two oxygen of the tetrahydrofurfuryl and one chlorine atom to form a distorted trigonal bipyramid.

Synthesis of substituted indenyl lanthanide chloride and molecular structure of [(C5H9C9H6)(2)Yb(mu-Cl)(2)Li(Et2O)(2)]

Reaction of anhydrous ytterbium trichlorides with 2 equiv. of cyclopentylindenyl lithium in THF solution, followed by removal of the solvent MO. crystallization of the product from diethyl ether, affords a crystal complex of the composition (C5H9C9H6)(2)Yb(mu-Cl)(2)Li(Et2O)(2). Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenyl rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb, U and two chlorine atoms form a plane.

Synthesis and structural characterization of organolanthanide complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands

Reactions of anhydrous LnCl(3) (Ln = Nd, Gd, Dy, Er, Yb) with 2 equiv of LiCp' in THF afford the lanthanocene complexes Of CP'(2)Ln(mu-Cl)(2)Li(THF)(2) (CP' = eta(5)-t-BuC5H4, Ln = Nd (1), Gd (2), Dy (3), Er (4), Yb (5); Cp'= 1,3-eta(5)-t-Bu2C5H3, Ln = Nd (6), Gd (7), Dy (8), Er (9), Yb (10)). The molecular structures of 7 and 8 were characterized by X-ray crystallographic analysis. In these complexes, two Cp' ring centroids and two it-bridging chloride atoms around the lanthanide atoms form a distorted tetrahedron. The insertion of elemental chalcogen E (E = S, Se) into Li-C bonds of dilithium o-carborane in THF solution afforded dimers of dilithium. dichalcogenolate carboranes, [(THF)(3)LiE2C2B10H10Li(THF)](2) (E = S (12a), Se (12b)), which were confirmed by a crystal structure analysis. Reactions Of Cp'(2)Ln(mu-Cl)(2)Li(THF)(2) (1-10) with 12a or 12b gave dinuclear complexes of the formula [Li(THF)(4)](2)[Cp'(2)LnE(2)C(2)B(10)H(10)](2) (Cp'= eta(5)-t-BuC5H4, E = S, Ln = Nd (13a), Gd (14a), Dy (15a), Er (16a), Yb (17a); E = Se, Ln = Nd (13b), Gd (14b), Dy (15b), Er (16b), Yb (17b); Cp'= 1,3-eta(5)-t-Bu2C5H3 E = S, Ln = Nd (18a), Gd (19a), Dy (20a), Er (21a), Yb (22a); E = Se, Ln = Nd (18b), Gd (19b), Dy (20b), Er (21b), Yb (22b)). According to the X-ray structure analyses, the dianions of 13a and 13b contain two o-carborane dichalcogenolate bridges, and each CP'2Ln fragment is attached to one terminal and two bridging chalcogen ligands. The central Ln(2)E(2) four-membered ring is not planar, and the direct metal-metal interaction is absent.

Synthesis and characterization of novel lanthanocene complexes with dichalcogenolate o-carboranyl ligands

Reactions of [ Cp(2)Ln(mu-Cl)](2) (Cp = eta(5)-C5H5, Ln = Nd, Yb, Dy, Gd, Er) with an equivalent of [ (THF)(3)LiE2C2B10H10Li. (TT-IF) (THF)](2) (E = S, Se) in THF afforded the dinuclear sandwich complexes of formula[Cp(2)LnE(2)C(2)B(10)H(10)](2)[Li(THF)(4)](2) [E = S, Ln = Nd (1a), Yb (2a), Dy (3a), Gd (4a), Er (5a); E = Se, Ln = Nd (1b), Yb (2b), Dy (3b), Gd (4b), Er (5b)]. The molecular structures of complexes la, 2a and 2b were determined by the single crystal X-ray structure analyses. Two lanthanide atoms are connected by a pair chalcogen (eta(1), eta(2)-E2C2B10H10) bridging ligands and the central Ln(2)E(2) four membered ring is not planar.

Synthesis of bis [bis (tert-butylcyclopentadienyl) neodymium chloride] and structural trend of bis[bis(tertbutylcyclopentadienyl) lanthanide chloride]

The reaction of NdCl3 with 2 equiv. of Na-(BuC5H4)-C-t in THF(tetrahydrofuran) gives blue crystals [((BUC5H4)-C-t)(2)NdCl](2), C36H52Cl2Nd2(M-r = 844.11) Which crystallizes in the triclinic system with space group . The crystal data are a=11.978 (1), b=12.671(4), c=12.706(2)Angstrom, alpha=105.47(2), beta=99.38(1)? gamma=93.15 (2)degrees, V=1825 (3) Angstrom(3), Z = 2 , D-c = 1.53g/cm(3), F(000) = 450 , T = 298K , lambda(MoK alpha) = 0.71069 Angstrom, , mu = 14.97cm(-1). Final R = 0.0390, R-w = 0.0376 for 4329 reflections with I greater than or equal to 3 sigma(I-o). The molecule has a dimer structure with two certrosymmetrical chlorine bridges. The structural trend of these analogous complexes is discussed.

Synthesis, crystal structure and luminescence studies of a lanthanide coordination polymer with a new double betaine ligand

A novel europium(III) coordination polymer with a new double betaine derivative, {[Eu(L')(NO3)(H2O)(3)](NO3)(2). 3.5H(2)O}(n) (L-1 = 1,3-bis(pyridinio-4-carboxylato)-propane) has been synthesized and its structure determined. Its luminescence properties have also been studied. The title metal carboxylate coordination polymer contains centrosymmetric dimeric units in which each pair of metal ions is linked by a pair of syn-anti carboxylato-O,O' groups, and each pair of such dimeric units is bridged by the backbones of L-1 ligands to form infinite double chains in the b direction. These metal carboxylate chains are further cross-linked by hydrogen bonds among both coordinated and discrete nitrate anions, aqua ligands and lattice water molecules to form a three-dimensional network. Luminescent data show that the L-1 ligand is a good energy donor and the complex has a relatively long luminescent lifetime.

Syntheses of indenyl lanthanide derivatives and the molecular structures of [(C9H7)(2)PrCl(THF)](2) and [(C9H7)(3)La(THF)]

The reaction of anhydrous PrCl3 with Na(C9H7) in 1.2 mole ratio in THF gives [(C9H7)(2)PrCl(THF)](2)1. 1 crystallized in monoclinic system, space group P2(1)/c with a = 7.808(2), b = 17.796(6), c = 14.070(4) Angstrom, beta = 93.97(2)degrees, V= 1950.3(9) Angstrom(3), Dcalcd = 1.63 g/cm(3) and Z = 2. Each Pr ion is surrounded by two indenyl, two Cl and one THF in a roughly trigonal bipyramid arrangement with average Pr-C(ring) and Pr-Cl distances of 2.81 and 2.84 Angstrom. The reaction of LaCl3 with Na(C9H7) in 1:3 mole ratio gives (C9H7)(3)LaTHF 2, which crystallizes in the monoclinic space group P2(1)/a with unit cell constants a = 21.871(8), b = 10.585(3), c = 23.652(7) Angstrom,beta = 114.62(2)degrees, V = 4977.9 Angstrom(3) and Z = 8. (C) 1997 Elsevier Science S.A.