Design, synthesis, and chemistry of sterically nondemanding primary bisphosphines

Design and synthesis of chelating bisphosphines functionalized with the smallest chemical unit "H" on the P(III) centers ((PH(2)CH(2))(2)CHCH(2)NHPh (4) and (PH(2)CH(2))(2)CHCONHPh (5)) are described. Studies demonstrating that no bulky chemical substituents are necessary to offer thermal/oxidative stability to the -PH(2) groups in 4 and 5 are described. The H atoms around the P(III) centers in 5 (or 4) concur limited/no steric influence, but yet the phosphines manifest high nucleophilicity to coordinate strongly with W(0) and Re(I). The studies include synthesis and X-ray structural characterization of an air-stable primary bisphosphine (5) and its transition-metal chemistry with W(CO)(6) and Re(CO)(5)Br to produce the complexes (eta(2)-(PH(2)CH(2))(2)CHCONHPh)W(CO)(4) (6) and (eta(2)-(PH(2)CH(2))(2)CHCONHPh)Re(CO)(3)Br (7), respectively.