Issue 14, 2016

Amino group combined P/Ge and P/Sn Lewis pairs: synthesis and dipolar addition reactions to alkyne and aldehyde molecules

Abstract

Amino group combined P/Ge-based frustrated Lewis pairs (FLPs) Ph2PN(R)GeCl3 (R = 2,6-iPr2C6H3 (1), 2,4,6-Me3C6H2 (2), and C6H11 (3)) and Ph2PN(2,6-iPr2C6H3)GeMe3 (4) as well as P/Sn-based FLP Ph2PN(2,6-iPr2C6H3)SnMe3 (5) were prepared and utilized for reactions with alkyne and aldehyde molecules. Compounds 1–3 each reacted with MeO2CC[triple bond, length as m-dash]CCO2Me to give zwitterionic cyclic vinyls [Ph2PN(R)GeCl3](MeO2CC[double bond, length as m-dash]CCO2Me) (6–8) and compound 1 reacted with HC[triple bond, length as m-dash]CCO2Me to give the similar compound [Ph2PN(2,4,6-Me3C6H2)GeCl3](HC[double bond, length as m-dash]CCO2Me) (9). Compound 4 reacted with RC[triple bond, length as m-dash]CCO2Me to afford acyclic vinyls 2,6-iPr2C6H3N[double bond, length as m-dash]P(Ph2)C(R)[double bond, length as m-dash]C(CO2Me)GeMe3 (R = CO2Me (10), H (11)) and 5 reacted with MeO2CC[triple bond, length as m-dash]CCO2Me to give 2,6-iPr2C6H3N[double bond, length as m-dash]P(Ph2)C(CO2Me)[double bond, length as m-dash]C(CO2Me)SnMe3 (12). The reactions of 1 with CH3CH2CHO and 1,4-(CHO)2C6H4 were also investigated and yielded novel zwitterionic OCPNGe five-heteroatom cycles [Ph2PN(2,6-iPr2C6H3)GeCl3][CH(CH2CH3)O] (13) and [Ph2PN(2,6-iPr2C6H3)GeCl3][p-(OCH)C6H4CHO][Cl3GeN(2,6-iPr2C6H3)PPh2] (14). Compounds 1–14 were characterized by NMR (1H, 13C, and 31P) and CHN elemental analysis, of which 1, 7, and 10–14 were further studied by X-ray crystallography. The reactions of 4 (or 5) with RC[triple bond, length as m-dash]CCO2Me to produce 10–12 present a novel way of obtaining the germyl (or stannyl) and iminophosphoranyl co-substituted vinyls.

Graphical abstract: Amino group combined P/Ge and P/Sn Lewis pairs: synthesis and dipolar addition reactions to alkyne and aldehyde molecules

Supplementary files

Article information

Article type
Paper
Submitted
04 Қаз. 2015
Accepted
30 Қар. 2015
First published
02 Жел. 2015

Dalton Trans., 2016,45, 6259-6268

Amino group combined P/Ge and P/Sn Lewis pairs: synthesis and dipolar addition reactions to alkyne and aldehyde molecules

Y. Yu, J. Li, W. Liu, Q. Ye and H. Zhu, Dalton Trans., 2016, 45, 6259 DOI: 10.1039/C5DT03873A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements