Structure and metal coordination of the diphosphine 2,2′-bis((diphenylphosphino)methyl)-1,1′-binaphthyl (NAPHOS)

Article abstract of DOI:10.1021/om00004a057

The crystal structure of the diphosphine 2,2′-bis((diphenylphosphino)methyl)-1,1′-binaphthyl (1, NAPHOS) has been determined by means of an X-ray diffraction study. The compound crystallizes in the triclinic space group P1 with a = 10.568(1) ?, b = 10.737(1) ?, c = 15.986(1) ?, α = 81.63(1)°, β = 86.42(1)°, γ = 81.47(1)°, V = 1773 ?³, and Z = 2. The metal complex Mo(CO)₄(NAPHOS) (4) crystallizes in the space group P2₁/c with a = 11.064-(3) ?, b = 15.931(2) ?, c = 28.462(8) ?, β = 100.67(1)°, V = 4930 ?³, and Z = 4. Molecular mechanics (MM) calculations for both Mo(CO)₄(NAPHOS) (4) and Mo(CO)₄(BISBI) (5) show an excellent match with the experimentally determined structures. A molecular dynamics (MD) simulation is demonstrated to be an efficient tool to sample over the accessible conformational space in order to cope with the global minimum problem . The dynamic behavior of these compounds in solution is also explainable on this basis.