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  • Synthesis of Crystallographically Characterizable Bis(cyclopentadienyl) Sc(II) Complexes: (C 5 H 2 t Bu 3 ) 2 Sc and {[C 5 H 3 (SiMe 3 ) 2 ] 2 ScI} 1–
Title: Synthesis of Crystallographically Characterizable Bis(cyclopentadienyl) Sc(II) Complexes: (C 5 H 2 t Bu 3 ) 2 Sc and {[C 5 H 3 (SiMe 3 ) 2 ] 2 ScI} 1–
The synthesis of previously unknown bis(cyclopentadienyl) complexes of the first transition metal, i.e., Sc(II) scandocene complexes, has been investigated using C5H2(tBu)3 (Cpttt), C5Me5 (Cp*), and C5H3(SiMe3)2 (Cp″) ligands. Cpttt 2ScI, 1, formed from ScI3 and KCpttt, can be reduced with potassium graphite (KC8) in hexanes to generate dark-red crystals of the first crystallographically characterizable bis(cyclopentadienyl) scandium(II) complex, Cpttt 2Sc, 2. Complex 2 has a 170.6° (ring centroid)-Sc-(ring centroid) angle and exhibits an eight-line EPR spectrum characteristic of Sc(II) with Aiso = 82.6 MHz (29.6 G). It sublimes at 200 °C at 10−4 Torr and has a melting point of 268−271 °C. Reductions of Cp*2ScI and Cp″2ScI under analogous conditions in hexanes did not provide new Sc(II) complexes, and reduction of Cp*2ScI in benzene formed the Sc(III) phenyl complex, Cp*2Sc(C6H5), 3, by C−H bond activation. However, in Et2O and toluene, reduction of Cp*2ScI at −78 °C gives a dark-red solution, 4, which displays an eight-line EPR pattern like that of 1, but it did not provide thermally stable crystals. Reduction of Cp″2ScI, in THF or Et2O at −35 °C in the presence of 2.2.2-cryptand, yields the green Sc(II) metallocene iodide complex, [K(crypt)][Cp″2ScI], 5, which was identified by X-ray crystallography and EPR spectroscopy and is thermally unstable. The analogous reaction of Cp*2ScI with KC8 and 18-crown-6 in Et2O gave the ligand redistribution product, [Cp*2Sc(18- crown-6-κ2O,O′)][Cp*2ScI2], 6, as the only crystalline product. Density functional theory  more » « less
Award ID(s):
2154255 2102568
PAR ID:
10506403
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
146
Issue:
5
ISSN:
0002-7863
Page Range / eLocation ID:
3279 to 3292
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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