title: Electronic and steric effects on molecular dihydrogen activation in [CpOsH4(L)]+ (L = PPh3, AsPh3, and PCy3).
abstract: Single-crystal neutron diffraction, inelastic neutron scattering, and density functional calculations provide experimental and theoretical analyses of the nature of the osmium-bound, "elongated" dihydrogen ligands in [Cp*OsH(4)(L)][BF(4)] complexes (L = PPh(3), AsPh(3), or PCy(3)). The PPh(3) and AsPh(3) complexes clearly contain one dihydrogen ligand and two terminal hydrides; the H(2) ligand is transoid to the Lewis base, and the H-H vector connecting the central two hydrogen atoms lies parallel to the Ct-Os-L plane (Ct = centroid of Cp* ring). In contrast, in the PCy(3) complex the H-H vector is perpendicular to the Ct-Os-L plane. Not only the orientation of the central two hydrogen atoms but also the H-H bond length between them depends significantly on the nature of L: the H...H distance determined from neutron diffraction is 1.01(1) and 1.08(1) A for L = PPh(3) and AsPh(3), respectively, but 1.31(3) A for L = PCy(3). Density functional calculations show that there is a delicate balance of electronic and steric influences created by the L ligand that change the molecular geometry (steric interactions between the Cp* and L groups most importantly change the Ct-Os-L angle), changing the relative energy of the Os 5d orbitals, which in turn govern the H-H distance, preferred H-H orientation, and rotational dynamics of the elongated dihydrogen ligand. The geometry of the dihydrogen ligand is further tuned by interactions with the BF(4)(-) counterion. The rotational barrier of the bound H(2) ligand in [Cp*OsH(4)(PPh(3))](+), determined experimentally (3.1 kcal mol(-)(1)) from inelastic neutron scattering experiments, is in reasonable agreement with the B3LYP calculated H(2) rotational barrier (2.5 kcal mol(-)(1)).
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, Texas 77842-3012, USA.
authors.forename: Charles Edwin
authors.initials: CE
authors.lastname: Webster
authors.forename: Christopher L
authors.initials: CL
authors.lastname: Gross
authors.forename: Dianna M
authors.initials: DM
authors.lastname: Young
authors.forename: Gregory S
authors.initials: GS
authors.lastname: Girolami
authors.forename: Arthur J
authors.initials: AJ
authors.lastname: Schultz
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall
authors.forename: Juergen
authors.initials: J
authors.lastname: Eckert