Calorimetric studies of the heats of protonation of the dangling phosphorus in [eta][sup 1]-Ph[sub 2]PCH[sub 2]PPh[sub 2] complexes of chromium, molybdenum, and tungsten

Journal Article · Wed May 26 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00063a036· OSTI ID:6000616

Rottink, M K; Angelici, R J ^[1]

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1. Iowa State Univ., Ames (United States)

Titration calorimetry has been used to determine the heats of protonation ([Delta]H[sub HP]) of M(CO)[sub 5]([eta][sup 1]-dppm) (M = Cr, Mo, W) and fac-M(CO)[sub 3](N-N)([eta][sup 1]-dppm) (M = Mo, N-N = bipy, phen; M = w, N-N = bipy) complexes with CF[sub 3]SO[sub 3]H in 1,2-dichloroethane solvent at 25.0 [degrees]C. Spectroscopic studies show that protonation occurs at the uncoordinated phosphorus atom of the [eta][sup 1]-coordinated dppm (Ph[sub 2]PCH[sub 2]PPh[sub 2]) ligand. For dppm, its monoprotonated form (dppmH[sup +]), and these complexes, the basicity ([Delta]H[sub HP]) of the dangling phosphorus increases from -14.9 kcal/mol to -23.1 kcal/mol in the order: dppmH[sup +]

• OSTI ID: 6000616
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:11; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINES
BARYONS
CALORIMETRY
CHROMIUM COMPLEXES
COMPLEXES
ELEMENTARY PARTICLES
ENTHALPY
FERMIONS
HADRONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
MOLYBDENUM COMPLEXES
NUCLEONS
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
PROTONS
REACTION HEAT
THERMODYNAMIC PROPERTIES
TITRATION
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES