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 Okt 2015
Accepted
30 Nov 2015
First published
02 Dez 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

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