Novel sulfur dioxide coordination in nitrosyl(sulfur dioxide)bis(triphenylphosphine)rhodium and an oxygen-18 study of its reaction with molecular oxygen

Journal Article · Sat Oct 01 00:00:00 EDT 1977 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50176a009· OSTI ID:7285894

Moody, D C; Ryan, R R

Crystals of Rh(NO)(SO/sub 2/)(PPh/sub 3/)/sub 2/ have been obtained from SO/sub 2/-saturated solutions of Rh(NO)(PPh/sub 3/)/sub 3/, and the structure has been determined at 25/sup 0/C. The compound crystallizes in the orthorhombic space group Pbca with a = 10.338 (2) A, b = 18.500 (4) A, c = 33.933 (7) A, d/sub c/ = 1.48 g cm/sup -3/, d/sub m/ = 1.47 g cm/sup -3/, and Z = 8 (Cu K..cap alpha../sub 1/ radiation, lambda 1.540 51 A). The structure refined to an unweighted R value of 0.038 for 2615 reflections with I > 2sigma(I). The SO/sub 2/ binds to the metal both through the sulfur atom and through one oxygen atom with a Rh-S distance of 2.326 (2) A and a Rh--O(2) distance of 2.342 (5) A. The S--O(2) distance of 1.493 (5) A is considerably longer than the S--O(1) distance of 1.430 (5) A, while the O(1)--S--O(2) angle is 115.1 (4)/sup 0/. The RhNO unit in this structure is clearly bent with a Rh--NO angle of 140.4 (6)/sup 0/. The factors influencing the bending of the nitrosyl are discussed in terms of the metal coordination geometry and number of d electrons. The mechanism of the reaction of this S,O-bonded SO/sub 2/ with molecular oxygen to form coordinated sulfate has been studied utilizing oxygen-18 substitution and infrared analysis. This study has revealed a distribution of the labeled oxygen in the resulting Rh(NO)(SO/sub 4/)(PPh/sub 3/)/sub 2/ different from that observed for S-bonded SO/sub 2/ reactions with molecular oxygen.

• Research Organization: Los Alamos Scientific Lab., NM
• OSTI ID: 7285894
• Journal Information: Inorg. Chem.; (United States), Vol. 16:10
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
NITROSO COMPOUNDS
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
ORGANIC SULFUR COMPOUNDS
OXYGEN
RHODIUM COMPLEXES
LATTICE PARAMETERS
PHOSPHINES
SULFUR DIOXIDE
CHALCOGENIDES
COMPLEXES
CRYOGENIC FLUIDS
ELEMENTS
FLUIDS
NONMETALS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
SULFUR COMPOUNDS
SULFUR OXIDES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties