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Synthesis and properties of SMAPs 1-phospha-4-silabicyclo[2.2.2]octane derivatives

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Title: Synthesis and properties of SMAPs 1-phospha-4-silabicyclo[2.2.2]octane derivatives
Authors: Ochida, Atsuko Browse this author
Sawamura, Masaya Browse this author
Keywords: Trialkylphosphines
phosphine selenides
electrostatic potential minimum
Issue Date: 9-Feb-2006
Publisher: ARKAT USA, INC.
Journal Title: ARKIVOC
Volume: 2006
Start Page: 359
End Page: 369
Abstract: Synthesis and properties of a new class of trialkylphosphine ligands SMAPs (1-phospha-4-silabicyclo[2.2.2]octane derivatives, named after silicon-constrained monodentate alkylphosphine) with Me3P-like steric demand around the phosphorus center are described. A new feature of this class of ligands is the presence of a site for functionalization at the backside of the P-lone pair, which is not the case for Me3P. The SMAP ligands contain phosphorus and silicon atoms at each bridgehead of the bicyclo[2.2.2]octane framework. The molecular constraint of the bicyclic framework makes the steric demand around the phosphorus center as small as that of Me3P and projects the P-lone pair and the Si-substituent (R) in diametrically opposite directions on the straight line defined by the two bridgehead atoms. SMAP derivatives bearing Si substituents with varied electronic natures are obtainable by transforming the parent compound 4-phenyl-phospha-4-silabicyclo[2.2.2]octane (Ph-SMAP) through Si–Ph bond cleavage, and they constitute a class of electronically tunable trialkylphosphines. DFT calculations indicated that the parent ligand Ph-SMAP is similar to Me3P in donor power and that the tunable range of the donor power overlaps those of (t-Bu)3P and RAr2P (R: alkyl, Ar: aryl).
Description: Part (vii): Special Issue Plenary and Invited Lectures ICHC-20
Type: article
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 澤村 正也

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