Bis(phosphine) derivatives of diamines

The synthesis, oxidation and coordination chemistry of new bis(aminophosphines) based on diamines is demonstrated. Ph2PN(CH2Ph)CH2CH2(CH2Ph)NPPh2, iPr2PN(CH2Ph)CH2CH2(CH2Ph)NPiPr2, Ph2PNH(C10H6)2NHPPh2, Ph2PNH(C10H6)(C6H4)NHPPh2 were prepared and tested in the hydroformylation of hex-1-to give aldehydes with poor selectivity (up to l:b=2.5:1) to the desired linear products. Modelling calculations were performed for all ligands. R2 groups enlarge the natural bite angle when going from R2=Ph2 to R2=iPr2 which are more bulky. Most of the ligands seem to be rigid (with flexibility ranges of 25°–46°). Four demonstrative X-ray structures are reported. [Copyright &y& Elsevier]