Asymmetric Synthesis and Metal Complexes of a C3-Symmetric P-Stereogenic Triphosphine, (R)-MeSi(CH2PMe(t-Bu))3 (MT-Siliphos)

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• 作者：Matthew F. Cain ; David S. Glueck ; James A. Golen ; Arnold L. Rheingold
• 刊名：Organometallics
• 出版年：2012
• 出版时间：February 13, 2012
• 年：2012
• 卷：31
• 期：3
• 页码：775-778
• 全文大小：328K
• 年卷期：v.31,no.3(February 13, 2012)
• ISSN：1520-6041

文摘

Asymmetric deprotonation of PMe₂(t-Bu)(BH₃) with s-BuLi/(鈭?-sparteine, followed by treatment with MeSiCl₃, gave a 2.6:1 mixture of the C₃- and C₁-symmetric triphosphine鈥揵oranes MeSi(CH₂PMe(t-Bu)(BH₃))₃ (3). Recrystallization gave highly diastereomerically and enantiomerically enriched C₃-3. After deprotection with morpholine, the triphosphine (R)-MeSi(CH₂PMe(t-Bu))₃ (4; (Me, t-Bu)-Siliphos or MT-Siliphos) was used to prepare the metal complexes [Rh(MT-Siliphos)(norbornadiene)][OTf] (5), Ru(MT-Siliphos)(DMSO)Cl₂ (6), [Ru(MT-Siliphos)(NCMe)₃][OTf]₂ (7), M(MT-Siliphos)(PPh₃) (M = Pd (8), Pt (9)), Cu(MT-Siliphos)(Cl) (10), and polymeric [Cu₂Cl₂(渭-(魏²,魏¹)-MT-Siliphos)]_{鈭?/sub> (11). The crystal structures of C3-3 and of complexes 5, 7, and 11 were determined, and dynamic processes in 6 and 8 were characterized by variable-temperature NMR spectroscopy.}