Coordination of the Aryldiazo Ligand to Transition Metals. Structure of Chloro(bis(3-diphenylphosphinopropyl)Phenylphosphine)Phenyldiazorhodium Hexafluorophosphate Methylene Chloride Solvate, [Rh(C6H5P((CH2)3P(C6H5)2)2)Cl(N2C6H5)][PF6]-CH2Cl2

Arthur P. Gaughan, James A Ibers

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Abstract

The structure of [RhLCl(N6C6H5)] [PF6] where L = the tridentate phosphine ligand C6PH5P((CH2)3P(C6H5)2)2 has been determined from three-dimensional X-ray counter data collected on a single crystal of the CH2Cl2 solvate. The material crystallizes in space group Ci'-P1 of the triclinic system with two formula units of the complex and two solvent molecules in a cell of dimensions a = 12.675 (7) Å, b = 13.254 (7) Å, c = 15.092 (10) Å, α = 94.78 (5)°, β = 99.47 (5)°, γ = 112.40 (8)°, and V = 2282.3 Å3. The observed and calculated (Z = 2) densities are 1.50 (1) and 1.507 g/cm3, respectively. The structure has been refined (on F) by a full-matrix least-squares procedure to a conventional agreement index of 0.057 for 4031 observations having Fo2 > 3σ(Fo2). The structural results reveal an ionic complex consisting of [RhLCl(N2Ph)] + cations (Ph = C6H5) and PF6- anions. The geometry of the cation is distorted tetragonal pyramidal with a basal plane consisting of the chloro ligand and the three P atoms of the tridentate phosphine. The apical coordination site is occupied by a doubly bent aryldiazo ligand and thus affords the first structural example of the aryldiazo analog of NO-, N2Ph-. The doubly bent geometry suggests formulation of the complex as the oxidative adduct of N2Ph+ to RhILCl yielding [RhIIILCl(N2Ph)]+. Distances and angles of interest within the cation are as follows: Rh-P, 2.368 (3), 2.274 (3), 2.352 (3) A; Rh-Cl, 2.403 (2) Å; Rh-N(l) (a to Rh), 1.961 (7) Å; N(1)‒N(2), 1.172 (9) Å; N(2)‒C(7) (Ph), 1.445 (11) Å; Rh-N(l)‒N(2), 125.1 (6)°; N(l)‒N(2)‒C(7), 118.9 (8)°. The structural results are compared with those for the corresponding NO complex, [RhLCl(NO)]+, and with the parent complex, RhLCl. The implications of the nitrosyl-aryldiazo analogy are discussed.

Original languageEnglish (US)
Pages (from-to)352-359
Number of pages8
JournalInorganic chemistry
Volume14
Issue number2
DOIs
StatePublished - Feb 1 1975

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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