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

Asymmetric deprotonation of PMe2(t-Bu)(BH3) with s-BuLi/(−)-sparteine, followed by treatment with MeSiCl3, gave a 2.6:1 mixture of the C 3- and C 1-symmetric triphosphine–boranes MeSi(CH2PMe(t-Bu)(BH3))3 (3). Recrystallization gave highly diastereomerically and enantiomerically enriched C 3-3. A...

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Veröffentlicht in:	Organometallics 2012-02, Vol.31 (3), p.775-778
Hauptverfasser:	Cain, Matthew F, Glueck, David S, Golen, James A, Rheingold, Arnold L
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creator	Cain, Matthew F Glueck, David S Golen, James A Rheingold, Arnold L
description	Asymmetric deprotonation of PMe2(t-Bu)(BH3) with s-BuLi/(−)-sparteine, followed by treatment with MeSiCl3, gave a 2.6:1 mixture of the C 3- and C 1-symmetric triphosphine–boranes MeSi(CH2PMe(t-Bu)(BH3))3 (3). Recrystallization gave highly diastereomerically and enantiomerically enriched C 3-3. 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(μ-(κ2,κ1)-MT-Siliphos)]∞ (11). The crystal structures of C 3-3 and of complexes 5, 7, and 11 were determined, and dynamic processes in 6 and 8 were characterized by variable-temperature NMR spectroscopy.
doi_str_mv	10.1021/om200930k
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Recrystallization gave highly diastereomerically and enantiomerically enriched C 3-3. 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(μ-(κ2,κ1)-MT-Siliphos)]∞ (11). 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Recrystallization gave highly diastereomerically and enantiomerically enriched C 3-3. 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(μ-(κ2,κ1)-MT-Siliphos)]∞ (11). 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