Organometallic compounds of the Lanthanides. 110. Donor-functionalized chiral cyclopentadienyl complexes of calcium, samarium(II), and ytterbium(II). A new class of chiral metallocenes

Journal Article · Tue Sep 03 00:00:00 EDT 1996 · Organometallics

DOI:https://doi.org/10.1021/om9603474· OSTI ID:380894

Molander, G A ^[1]; Schumann, H; Rosenthal, E C.E.; Demtschuk, J ^[2]

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1. Univ. of Colorado, Boulder, CO (United States)
2. Technischen Universitaet Berlin (Germany)

Twelve optically active metallocene complexes of Ca, Sm(II), and Yb(II) containing cyclopentadienyl systems with a chiral N- or O-substituted side chain as ligands are described. Specifically, the ligand systems (S)-(2-methoxypropyl)cyclopentadienyl ((S)-C{sub 5}H{sub 4}-CH{sub 2}CH(Me)OMe) and (S)-(2-methoxy-2-phenylethyl)cyclopentadienyl ((S)-C{sub 5}H{sub 4}CH{sub 2}CH(Ph)OMe) and the novel (S)-[2-(dimethylamino)propyl]cyclopentadienyl ((S)-C{sub 5}H{sub 4}CH{sub 2}CH(Me)NMe{sub 2}) and (S)-[2-(dimethylamino)-1-phenylethyl]cyclopentadienyl ((S)-C{sub 5}H{sub 4}CH(Ph)CH{sub 2}NMe{sub 2}) systems were employed. The starting materials for their synthesis are ethyl(S)-(-)-lactate, (R)-(-)-2-methoxy-2-phenylethanol, (S)-(+)-2-amino-l-propanol, and (R)-(-)-2-phenylglycinol, respectively. Each of the cyclopentadienyl systems was converted by a 2:1 reaction of the potassium salt with the metal diiodide into the corresponding metallocene, [M[C@(S)-{eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}(CH{sub 2}CH(R) OMe)]C{sub 2}] (R = Me, M = Ca (1a), Sm (1b), Yb (1c); R = Ph, M = Ca (3a), Sm (3b), Yb (3c)), [M[C@(S)-{eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}(CH{sub 2}CH(Me)NMe{sub 2})]{sub 2}] (M = Ca (2a), Sm (2b), Yb (2c)), and [M[C@(S)-{eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}(CH(Ph)CH{sub 2}NMe{sub 2})]{sub 2}] (M=Ca (4a), Sm (4b), Yb (4c)). The novel compounds have been characterized by C, H, N analysis, mass spectrometry, NMR spectroscopy, and optical rotation. Additionally, an X-ray structural analysis of 2c, 3a, and 4a was performed. 21 refs., 4 figs., 7 tabs.

• OSTI ID: 380894
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 18 Vol. 15; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
BOND ANGLE
BOND LENGTHS
CALCIUM COMPLEXES
CHIRALITY
EXPERIMENTAL DATA
MASS SPECTRA
MOLECULAR STRUCTURE
NMR SPECTRA
OPTICAL PROPERTIES
ORGANOMETALLIC COMPOUNDS
SAMARIUM COMPLEXES
SYNTHESIS
X-RAY DIFFRACTION
YTTERBIUM COMPLEXES