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Crystal and Molecular Structures of the Functional Lithium Cyclopentadienides [Li(tmeda)][R

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Crystal and Molecular Structures of the Functional Lithium Cyclopentadienides [Li(tmeda)][R

2

PCMe

2

C

5

H

4

], R = Ph, Me Ulrich J¨urgen Bildmann, Martin Winkler, and Gerhard M¨uller

Fachbereich Chemie, Universit¨at Konstanz, Universit¨atsstr. 10, 78464 Konstanz, Germany Reprint requests to Prof. Dr. Gerhard M¨uller. E-mail: gerhard.mueller@chemie.uni-konstanz.de Z. Naturforsch.55 b,1005–1010 (2000); received August 21, 2000

Lithium Cyclopentadienides

The crystal and molecular structures of the phosphinomethyl-substituted lithium cyclopenta- dienides [Li(tmeda)][R2PCMe2C5H4], R = Ph (1), Me (2) (tmeda = N,N,N',N'-tetramethylethyl- enediamine) were determined as their tmeda adducts on the basis of low temperature single crystal X-ray diffraction. (Crystal data:1: monoclinic, space group P21/n, a = 8.511(5), b = 11.936(2), c = 24.20(1) ˚A,= 90.02(3), Z = 4.2: monoclinic, space group P21/n, a = 10.887(2), b = 13.326(2), c = 13.131(2) ˚A,= 92.872(6), Z = 4). In both compounds lithium has a slightly distorted5coordination to the cyclopentadienide (Cp) ring. There are no interactions between lithium and the phosphine donors in the solid state as the phosphinomethyl substituents are oriented to the other side of the Cp ring for steric reasons. The isopropene-substituted lithium cyclopentadienide, which is formed as a by-product in the synthesis of phosphinomethyl cyclo- pentadienides containing a CMe2bridge, was also structurally characterized as its tmeda adduct [Li(tmeda)][H2C=CMeC5H4] (3). (Crystal data: monoclinic, P21/c, a = 8.00(2), b = 16.701(2), c = 11.942(6) ˚A,= 112.68(7), Z = 4). As in1and2, lithium is5-coordinated to the Cp ring, and there is no interaction of the functional group (isopropene) with lithium.

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