title: Pseudotetrahedral manganese complexes supported by the anionic tris(phosphino)borate ligand [PhBP(iPr)3].
abstract: This paper presents aspects of the coordination chemistry of mono- and divalent manganese complexes supported by the anionic tris(phosphino)borate ligand, [PhBP(i)(Pr)3] (where [PhBP(i)(Pr)3] = [PhB(CH(2)P(i)Pr2)3]-). The Mn(II) halide complexes, [PhBP(i)(Pr)3]MnCl (1) and [PhBP(i)(Pr)3]MnI (2), have been characterized by X-ray diffraction, SQUID magnetometry, and EPR spectroscopy. Compound 2 serves as a precursor to a series of Mn azide, alkyl, and amide species: [PhBP(i)(Pr)3]Mn(N3) (3), [PhBP(i)(Pr)3]Mn(CH2Ph) (4), [PhBP(i)(Pr)3]Mn(Me) (5), [PhBP(i)(Pr)3]Mn(NH(2,6-(i)Pr2-C6H3)) (6), [PhBP(i)(Pr)3]Mn(dbabh) (7), and [PhBP(i)(Pr)3]Mn(1-Ph(isoindolate)) (8). The complexes 2-8 feature a divalent-metal center and are pseudotetrahedral. They collectively represent an uncommon structural motif for low-coordinate, polyphosphine-supported Mn complexes. Two Mn(I) species have also been prepared. These include the Tl-Mn adduct [PhBP(i)(Pr)3]Tl-MnBr(CO)4 (9) and the octahedral complex [PhBP(i)(Pr)3]Mn(CN(t)Bu)3 (10). Some of our initial synthetic efforts to generate [PhBP(i)(Pr)3]MnN(x) species are briefly described, as are DFT studies that probe the electronic viability of these types of multiply bonded target structures.
authors.affiliation: Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Connie C
authors.initials: CC
authors.lastname: Lu
authors.forename: Jonas C
authors.initials: JC
authors.lastname: Peters
mesh_terms: D000838:Anions; D001881:Borates; D004578:Electron Spin Resonance Spectroscopy; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines; D012238:Rhodium / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000838:Anions; D001881:Borates; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D012238:Rhodium