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 ((1)H, (13)C, and (31)P) 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.