Frank H. Görlitz

Synthesis and crystal structure of pentabenzylcyclopentadienylindium(I)

Abstract (PhCH 2 ) 5 C 5 In 1 ( 1 ) is formed in the reaction between InCl and (PhCH 2 ) 5 C 5 Li. 1 crystallizes in the space group P 2 1 / c with a 1022.8(1), b 1575.3(2), c 1871.3(3) pm, β 91.01(1)°, and V 3014.6 × 10 −30 m 3 . The crystal and molecular structure was solved to final values of R = 0.025 for 5545 observed reflections with F 0 ≥ 4σ ( F 0 ). The association of two single molecules, via a center of symmetry between the two In atoms, gives the impression of quasi-“dimeric” units with an InIn distance of 363.1 pm and predominantly covalent InC. 1 H NMR, 13 C NMR, infrared and mass spectroscopic data are reported.

Komplexkatalyse: XL. Darstellung und Kristallstruktur des Tetra(allyl)lanthanat(III)-Komplexes [Li(μ-C4H8O2)3/2][La(η3-C3H5)4], eines Katalysators für die stereospezifische Butadienpolymerisation☆

Abstract The title complex was synthesized by reaction of LaCl3, Sn(C3H5)4 and LiC4H9 in toluene and could be obtained as crystals in the form of the dioxane adduct from ether solution. Characterization was achieved by elemental analysis, IR-, 1H- and 13C-NMR-spectroscopy and X-ray crystal structure analysis. The π-bonded allyl groups are coordinated at the lanthanum with tetrahedral distortion. The lithium ions form wavy layers and each is bridged by three dioxane molecules. There is also a weak interaction with one terminal C-atom of one allyl group. Under standard conditions the complex has a moderately catalytic effect on the 1,4-trans polymerization of butadiene in toluene.

Metallorganische verbindungen der lanthanoide: LXX. Bis(cyclopentadienyl)seltenerdkomplexe: Synthese und röntgen-strukturanalyse von dem intramolekular stabilisierten lutetiumalkyl Cp2Lu(CH2)3NMe2 und dem monomeren basenfreien yttriumcarboxylat Cp2Y[η2-O2C(CH2)3NMe2]☆

Abstract Metathesis of LuCl3, NaCp and Li(CH2)3NMe2 in the molar ratio 1:2:1 affords the lutetium alkyl species Cp2 Lu(CH 2 ) 3 N Me2 (1); analogous reaction of LuCl3, NaMeC5H4 and LiCH2CH(Me)-CH2NMe2 generates the corresponding complex (MeC5H4)2 Lu[CH 2 CH(Me)CH 2 N Me2] (2). Treatment of YCl3 with two equivalents of NaCp and one equivalent of Li(CH)3NMe2 yields, in the presence of CO2, the yttrium carboxylate Cp2Y[η2-O2C(CH2)3NMe2 (3). Mass spectrometrical studies of the solvent-free rare earth triflates [Cp2Ln(OSO2CF3)]2 (Ln = Sc (4), Lu (5)) have shown them to be dimeric. The crystal structures of 1 and 3 were determined by X-ray diffraction methods. 1 crystallizes in the monoclinic space group P21 (No. 4) with the unit-cell parameters a 657.0(4), b 1386.7(8), c 803.5(3) pm, β 106.64(5)°, V 704(1) × 10−30 m3 and Z = 2. The structure was solved on the basis of 1094 observed reflections with F0 ≥ 3σ(F0) and refined to a final R value of 0.0483. With the short LuN bond length of 237(1) pm the molecular structure of 1 exhibits an intramolecular N → Lu coordination. The crystals of 3 are triclinic, space group P 1 (No. 2), with a 1078.2(6), b 1533.0(9), c 1020.3(8) pm, α 109.47(6), β 82.75(6), γ 88.99(5)°, V 1574(2)×10−30 m3 and Z = 4. Least-squares refinement of the model based on 1659 observed reflections converged to R = 0.093 (F0 ≥ 5σ(F0)). The structural data of 3 feature a monomer with a chelating carboxylate group. The long YN distance (499 pm) excludes any intramolecular NY interactions.

Metallorganische Verbindungen der Lanthanoide. LXXVIII: Bis(pentamethylcyclopentadienyl)[4-(1,2,3,4,5-pentamethylcyclopentadien-1-yl)butoxy](tetrahydrofuran)lanthanoide

Abstract LnCl 3 (LnLa, Nd, Tm, Lu) reacts with NaCp* (Cp*C 5 (CH 3 ) 5 ) in THF to yield the complexes Cp* 2 Ln[O(CH 2 ) 4 Cp*(THF) ( 1 = La, 2 = Nd, 3 = Tm, 4 = Lu). Crystals of 2 are monoclinic, space group C 2/ c with a 2999.8(6), b 1396.1(3), c 1740.0(3) pm, s 90.54(1)°, V 7287(3) × 10 −3 m 3 and Z = 8. Least-squares refinement on the basis of 4680 reflections ( F o >4σ( F o )) led to a final R value of 0.0268. 4 crystallizes monoclinic, space group C 2/ c with a 2965.4(5), b 1384.6(3), c 1740.6(4) pm, s 90.81(1)°, V 7146(3) × 10 −30 m 3 and Z = 8. Least- squares refinement on the basis of 4097 reflections ( F o >4σ( F o )) led to a final R value of 0.028.

Intramolekular stabilisierte gallium- und indiumorganyle: Synthese und röntgenstrukturanalyse repräsentativer bis- und tris[3-(dialkylamino) propyl]gallium- und -indium-derivate

Abstract The intramolecularly stabilized organogallium and organoindium compounds ClGa(CH 2 CH 2 CH 2 NMe 2 ) 2 ( 1 ), RIn(CH 2 CH 2 CH 2 NMe 2 ) 2 (R = Cl, Br, I, CN, SCN, CF 3 CC, MeCC, Me 3 SiCC, C 6 F 5 O, CF 3 CO 2 , CF 3 , i C 3 F 7 ,( 2a–13a ), RIn(CH 2 CH 2 CH 2 NEt 2 ) 2 (R = Cl, I, CN, CF 3 CC, MeCC, Me 3 SiCC, C 6 F 5 O, CF 3 CO 2 ( 2b , 4b , 5b , 7b–11b ) ClGa(C 6 H 4 CH 2 NMe 2 -2) 2 ( 14 ), ClIn(C 6 H 4 CH 2 NMe 2 -2) 2 ( 15 ), and ClIn[CH 2 CH 2 CH 2 N(CH 2 ) 5 ] 2 ( 16 ) a well as the homoleptic compounds GaR 3 (R = CH 2 CH 2 CH 2 NMe 2 ( 17 ), CH 2 CHMeCH 2 NMe 2 ( 18 ), C 6 H 4 CH 2 NMe 2 -2 ( 19 ) and In(CCCF 3 ) 3 (THF) 2 ( 20 ) have been synthesized from gallium trichloride or indium trichloride and the corresponding ω-aminoorganyl lithium compounds, by the reaction of 2a and 2b with the appropriate RLi, or from Cd(CH 2 CH 2 CH 2 NMe 2 ) 2 and RInBr 2 (R = CF 3 , i C 3 F 7 ). The 1 H-, 13 C-NMR and mass spectra of the new compounds as well as the X-ray crystal structure analyses of 1 , 4a , 14 , 17 , 19 and 20 are reported and discussed.

Reduction of vanadium(II) to vanadium(O) by naphthaleneytterbium: synthesis and X-ray crystal structure of the two-dimensional multidecker complex [(η5-C5H5)V(μ-η6:η2-C10H8)Yb(THF)-(η5-C5H5)]n

Abstract The reaction of (C 5 H 5 ) 2 V with an excess of (C 10 H 8 )Yb(THF) 2 in tetrahydrofuran at room temperature generated the polymeric two-dimensional multidecker complex [(η 5 -C 5 H 5 )V(μ-η 6 :η 2 -C 10 H 8 )Yb(THF)(η 5 -C 5 H 5 )] n , ( 1 ), which is also obtained from the reaction of YbI 2 (THF) 2 with an equimolar mixture of KC 5 H 5 and K[(C 5 H 5 )V(C 10 H 8 )] in tetrahydrofuran. The new compound was characterized by elemental analyses, magnetic susceptibility, IR and ESR spectra. The X-ray structural analysis of 1 showed the compound to be monoclinic, space group C2/c , Z =8, with a =19.07(5), b =13.61(3), c =17.40(3) A, β=91.9(2)° and D calc =1.84 g cm −3 . The structure was solved from 2482 observed reflections with F o > 4σ(F o ) and refined to a final R value of 0.047. The molecular structure consists of infinite zig-zag chains formed by (η 5 -C 5 H 5 )Yb moieties and with one (η 5 -C 5 H 5 )V(η 6 -C 10 H 8 ) unit coordinated η 2 via the naphthalene to each Yb atom.

Synthesis and characterization of Eu(II) and Sm(II) complexes containing the cyclopentadienylvanadiumnaphthalene anion. Molecular structure of [(C5H5)V(C10H8)2Eu(THF)(DME) and [(C5H5)V(C10H8)Eu(C5H5)(THF)]n]

Abstract The reaction of LnI2(DME)3 with an equimolar mixture of K(C5H5) and K(C5H5)V(C10H8) in DME followed by treatment with THF results in the formation of the tetradecker bimetallic complexes [(C5H5)V(C10H8)]2Ln(THF)(DME) with Ln = Eu (1) and Sm (2). Removal of the solvent and subsequent addition of THF leads to coordination polymers [(C5H5)V(C10H8Ln(C5H5)(THF)]n with Ln = Eu (3) and Sm (4). These novel complexes have been characterized by IR spectroscopy and the europium derivatives by X-ray crystallography. 1 is triclinic, space group P1 (No. 2), z =2, with a = 1203.6(4), b = 1280.8(6), c = 1140.8(3) pm, α = 91.37(4), β = 97.14(3), γ = 100.44(3)°. The structure was refined to R = 0.026 for 3027 observed reflections (Fo > 3σ (Fo)). It shows two (C5H5)Eu(C10H8) sandwich units η6-bonded to Eu via one six membered ring of the naphthalene with an additional THF and DME coordinated to europium. 3 is monoclinic, space group C2/c (no. 15), Z = 8, with a = 1916.0(3), b = 1330.4(3), c = 1765.3(4) pm, and β = 90.17(2)°. The structure was refined to R = 0.032 for 2734 observed reflections (Fo > 4σ (Fo)). It forms infinite polymeric zig-zag chains consisting of (C5H5)Eu units, in which the europium atoms are coordinated by an additional THF and (C5H5)V(C10H8) units which are each bonded η2 via a naphthalene.

Synthesis and X-ray crystal structure of cyclooctatetraenyllanthanide alkyl complexes [Li(thf)2{µ-(η2:η8-C8H8)}Ln{CH(SiMe3)2}2](Ln = Y, Sm, Lu; thf = tetrahydrofuran)

The metathetic reaction [Ln(η8-C8H8)(µ-Cl(thf)]2(Ln = Y, Sm, Lu) with LiCH(SiMe3)2results in the formation of the Cyclooctatetraenyllanthanide alkyl complexes [Li(thf)2{µ-+(η2;η8-C8H8)} Ln{CH (SiMe 3)2}2](Ln = Y1a, Sm1b, Lu1c); 1b has been structurally characterized by X-ray crystallography.

Synthesis, structure determination and immobilization of some dirhodium complexes with chiral binding thiolato ligands. Investigation of their catalytic activity for enantioselective hydrogenation

Abstract (−)-cis[Dicarbonyl-μ-chloro-[μ-6,6-dimethylbicyclo[3.1.1]heptane-2-methanethiolato-S:S)]]bis[tris(1,1-dimethylethyl)phosphine]dirhodium (5a) and (+)-cis-[dicarbonyl-μ-chloro-[μ-5β-methyl-2α-(1-methyl-ethyl)cyclohexanethiolato-S:S]]bis[tris(1,1-dimethylethyl)phosphine]dirhodium (5b) were prepared from [Rh(CO)2]2(μ-Cl)2, P(t-Bu)3 and the corresponding sulfides (−)-cis-(myrtanethio)trimethylsilane (4a) and (+)-(neomenthanethio)trimethylsilane (4b). The molecular structures of 5a and 5b were determined by single-crystal X-ray diffraction (5a: C2221, a = 13.749(4), b = 23.509(9), c = 27.271(9) A, Z = 8, R = 0.0443, Rw = 0.0491. 5b: P 1 , a = 16.209(6), b = 14.150(5), c=9.899(3) A, Z = 2, R = 0.058, Rw = 0.094). Complex 5b was found to exist in the crystal as a pair of 1R,2R,5S- and 1S,2R,5S-epimers. Both chiral complexes have been immobilized by attachment to divinylbenzene-crosslinked polystyrene resins. Application of the chiral dirhodium complexes as catalysts for hydrogenation of methyl α-acetamidocinnamate revealed that while 5b leads to optically active N-acetylphenylalanine methyl ester (up to 50% ee) 5a gives only the racemic product. The immobilization of the complexes proved to improve the enantioselectivity of 5a but decreases the ability of 5b to induce asymmetric reduction.

Metallorganische verbindungen der lanthanoide: LXXI. Synthese und röntgenstrukturanalyse von CpLa(C5H4PPh2)2(THF), einem zweizähnigen liganden zur herstellung heterobimetallischer lanthanoidkomplexe

LaCl3 reacts with TlC5H4PPh2 and NaCp in the molar ratio 1:2:1 to form the bidentate, monomeric tris(cyclopentadienyl) lanthanum derivative CpLa(C5H4PPh2)2(THF) (1). Crystals of 1 belong to the monoclinic space group P21/m with a = 870(1), b = 2000.9(5), c = 1016(1) pm, β = 93.03(5)°, V = 1772.4·10−30 m3 and Z = 2. Least-squares refinement on the basis of 1142 observed reflections (F0 > 3σ(F0)) led to a final R value of 0.047.