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Title: X-ray structure and reactivity of (Ru(bpy)/sub 2/(CO)H)PF/sub 6/ x 1/2 C/sub 3/H/sub 6/O (bpy = 2,2'-bipyridyl), a possible intermediate in the water-gas shift reaction catalyzed by ruthenium polypyridyl complexes

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00243a018· OSTI ID:6981344
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The structure of (Ru(C/sub 10/H/sub 8/N/sub 2/)/sub 2/(CO)H)PF/sub 6/ x 1/2 C/sub 3/H/sub 6/O is reported. The compound crystallizes in the monoclinic C2/c space group with unit cell parameters a = 26.680 (4) A, b = 7.005 (3) A, c = 25.936 (2) A, and ..beta.. = 93.96 (2)/sup 0/ (V = 4836.04 A/sup 3/, Z = 8). The cationic species has a cis geometry for CO and H. The ruthenium-hydride and ruthenium-carbon distances are 1.68 (4) and 1.804 (6) A, respectively. The average ruthenium-nitrogen distance is 2.109 A. In acidic solution the title compound acts as a hydride donor to produce dihydrogen gas in a pseudo-first-order reaction; the second-order rate constant for this reaction is 0.105 -/+ 0.01 dm/sup 3/ mol/sup -1/ s/sup -1/ at 303 K with an activation energy 56 -/+ 2 kJ mol/sup -1/. A value of -100 -/+ 8 J mol/sup -1/ deg/sup -1/ has been obtained for the entropy of activation. The consequences of these results for the possible reaction mechanism of the homogeneous water-gas shift reaction catalyzed by (Ru(bpy)/sub 2/(CO)Cl)/sup +/ are discussed. 15 references, 4 figures, 6 tables.

Research Organization:
National Institute for Higher Education, Dublin, Ireland
OSTI ID:
6981344
Journal Information:
Inorg. Chem.; (United States), Vol. 25:23
Country of Publication:
United States
Language:
English

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Related Subjects

08 HYDROGEN
BIPYRIDINES
ACTIVATION ENERGY
CRYSTAL STRUCTURE
CARBONYLS
ORGANOMETALLIC COMPOUNDS
PHOSPHORUS FLUORIDES
RUTHENIUM COMPOUNDS
WATER GAS PROCESSES
CATALYSIS
EXPERIMENTAL DATA
HYDROGEN PRODUCTION
X-RAY DIFFRACTION
AZINES
CHEMICAL REACTIONS
COHERENT SCATTERING
DATA
DIFFRACTION
ENERGY
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
PYRIDINES
REFRACTORY METAL COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPOUNDS
080104* - Hydrogen- Production- Water Gas Processes