One- and two-electron chemistry in the reaction of nitrogen dioxide and nitrosyl halides with binuclear pyrophosphito complexes of platinum(II) and platinum(III). [Nitrosyl halides and binuclear pyrophosphito complexes of platinum(II) and platinum(III)]

Journal Article · Wed Sep 25 00:00:00 EDT 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00214a013· OSTI ID:6243928

Hedden, D; Roundhill, D M; Walkinshaw, M D

Nitrogen dioxide adds to the bridged binuclear Pt(II)-Pt(II) complex Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/ to give the Pt(III)-Pt(III) complex Pt/sub 2/..sqrt..(P/sub 2/O/sub 5/H/sub 2/)/sub 4/(NO/sub 2/)/sub 2//sup 4 -/. The NO/sub 2/ ligands coordinate the axial positions in this Pt(III)-Pt(III) complex, and this has been confirmed by X-ray crystallography. Crystals grown from an acidic aqueous solution of Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/ and NaNO/sub 2/ have the formula H/sub 40/N/sub 2/O/sub 42/P/sub 8/Pt/sub 2/Na/sub 8/. The compound crystallizes in the monoclinic space group C2/c with a = 13.958 (3) A, b = 19.413 (2) A, c = 15.538 (5) A, ..beta.. = 106.19 (2)/sup 0/, and Z = 4. The molecular structure shows respective Pt-Pt and Pt-N distances of 2.7333 (3) and 2.153 (6) A, with half the ligand protons replaced by hydrated sodium ions. Reductive elimination of NO/sub 2/ gives Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/. Halide ion X/sup -/ (X = Cl, Br) reacts with Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4/(NO/sub 2/)/sub 2//sup 4 -/ to give Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4/X(NO/sub 2/)/sup 4 -/. Excess iodide ion gives Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4/I/sub 2//sup 4 -/, and 1 equiv of N-iodosuccinimide reacts with Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4/(NO/sub 2/)/sub 2//sup 4 -/ to give Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4/I(NO/sub 2/)/sup 4 -/. Nitric oxide does not add to Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/, and nitrosyl chloride gives Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4/Cl/sub 2//sup 4 -/. Carbonylation of Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4/(NO/sub 2/)/sub 2//sup 4 -/ gives CO/sub 2/ and Pt/sub 2/(P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/ with no observable nitrosyl intermediate. 25 references, 4 figures, 5 tables.

• Research Organization: Tulane Univ., New Orleans, LA
• OSTI ID: 6243928
• Journal Information: Inorg. Chem.; (United States), Vol. 24:20
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
NITROGEN DIOXIDE
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
PHOSPHORUS COMPLEXES
COORDINATION VALENCES
CRYSTALLOGRAPHY
ELECTRONS
EXPERIMENTAL DATA
LIGANDS
X-RAY DIFFRACTION
CHALCOGENIDES
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
ELEMENTARY PARTICLES
FERMIONS
INFORMATION
LEPTONS
NITROGEN COMPOUNDS
NITROGEN OXIDES
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
SCATTERING
VALENCE
400201* - Chemical & Physicochemical Properties