Lothar Esser

Binuclear complexes of La(III) and Eu(II) with the bridging naphthalene dianion. Synthesis and X-ray crystallographic analysis of [μ2-η4:η4-C10H8][LaI2(THF)3]2 and [μ2-η4:η4-C10H8][EuI(DME)2]2

Abstract The treatment of LaI 3 (THF) 3 with equimolar amounts of Li and excess of C 10 H 8 in THF results in the formation of [C 10 H 8 ][LaI 2 (THF) 3 ] 2 ( 1 ) and the reaction of EuI 2 (THF) 2 with Li and C 10 H 8 in DME leads to [C 10 H 8 ][EuI(DME) 2 ] 2 ( 2 ), which have been characterized by IR and UV-VIS spectroscopy as well as by X-ray crystallography. 1 is monoclinic, space group P 2 1 / c (No. 14), Z = 4, with a = 1314.2(6), b = 1256.7(5), c = 1697.2(4) pm, β = 93.53(3)°. The structure was refined to R = 0.045 for 2377 observed reflections( F 0 > 4 σ ( F 0 )). 2 is monoclinic, space group P 2 1 / n , Z = 4 with a = 1015.1(3), b = 1389.8(4), c = 1269.8(3) pm, β = 97.51(2)°. The structure was refined to R = 0.0408 for 2687 observed reflections ( F 0 > 4 σ ( F 0 )). Both molecules contain two LaI 2 (THF) ( 1 ) or EuI(DME) moieties ( 2 ), bridged η 4 each by a non planar naphthalene with dihedral angles of 15° ( 1 ) and 6° ( 2 ) respectively.

Notizen: The Bishydridobis(tetrazol-1-yl)borate Anion, [H2B(CHN4)2]-: Synthesis and Structure of the First Tetrazolylborate

Potassium bishydridobis(tetrazol-1-yl)borate (1) has been synthesized from KBH4 and tetrazole and characterized spectroscopically. Its crystal structure has been determined. 1 crystallizes in the monoclinic space group P21/n with a = 537.8(2), b = 1703.5(9), c = 919.6(3) pm, β = 106.12(3)° and V = 809.4(6)· 106 pm3.

1-[4- { 1,1′,1″,1‴-(1,3-Cyclopentadien-1,2,3,4-tetrayl)tetrakis} ]-(4,1-phenylen)-alkanone und deren Natrium-, Thallium(I)- und Fe(II)-Komplexe / 1-[4- { 1,1′,1″,1‴-(1,3-Cyclopentadiene-1,2,3,4-tetrayl)tetrakis} ](4,1 -phenylene)-alkanones and their Sodium, Thallium(I) and Iron(II) Complexes

Tetraphenylcyclopentadiene (1) reacts with acylchlorides RC(O)Cl (R = CH3, C3H7, C5H11,C7H15) to form the corresponding [(cyclopentadiene tetrayl)tetrakis] (4,1-phenylene)alkanones C5H2(C6H4C(O)R-4)4 (2a, 2b, 2c and 2d). 2a reacts with NaNH2 generating the corresponding sodium salt Na[C5H(C6H4C(O)R-4)4] (3a). 2a, 2b, 2c, and 2d react with T1OC2H5 yielding the thallium(I) derivatives Tl[C5H(C6H4C(O)R-4)4] (4a, 4b, 4c, 4d). Octaphenylferrocene (5) reacts with acylchlorides RC(O)Cl (R = CH3, C3H7, C5H11, C7H15) to form octaacylated ferrocenes Fe[C5H(C6H4C(O)R-4)4]2 (6a, 6b, 6c and 6d). 6a can also be prepared by reacting FeI2 with 3a. 6a reacts with NaOBr yielding Fe[C5H(C6H4C(O)OH-4)4]2 (7), which after reaction with C5H11OH and C7H15OH gives the corresponding octaesters Fe[C5H(C6H4C(O)OR-4)4]2 (8c and 8d). 6a and 6b are reduced by N2H4(H2O) to give Fe[C5H(C6H4CH2R-4)4]2 (11a and 11b). The X-ray crystal structures of tetraphenylcyclopentadiene (2 a), as well as of the partially and totally substituted ferrocene derivatives Fe[C5H(C6H4C(O)CH3-4)4][C5H(C6H4C(O)CH3-4)3(C6H5)] (9), Fe[C5H(C6H4C(O)C3H7-4)(C6H5)3]2 (10) and Fe[C5H(C6H4C4H9-4)4]2 (11b) have been determined. The 1H and 13C NMR spectra of the new compounds are reported and discussed.