Pentaammineruthenium(II) and pentaammineosmium(II) complexes of olefins and linear dienes related to 1,3-butadiene
(M(NH/sub 3/)/sub 5/(olefin))/sup 2 +/ complexes, M = Ru/sup II/ and Os/sup II/, have been prepared for the olefin series isobutylene, propene, 1,3-butadiene, 1,4-pentadiene, and 1,5-hexadiene. These complexes have been characterized by /sup 1/H NMR spectroscopy and differential-pulse voltammetry. Protons directly attached to the coordinated olefin moiety exhibit upfield /sup 1/H shifts of 1.5-2.5 ppM vs the free ligand for Ru/sup II/. The Os/sup II/ derivatives are shifted an additional 15% upfield. The E/sub 1/2/ values of the Ru/sup III/II/ complexes are 0.65-0.88 V more positive of the NH/sub 35/RuOH/sub 2//sup 3+/2+/ couple; the Os/sup III/II/ couples are shifted ca. 1.1 V relative to (NH/sub 3/)/sub 5/OsOH/sub 2//sup 3+/2+/. Both the upfield /sup 1/H NMR shifts of coordinated olefin protons and E/sub 1/2/ values implicate very strong back-donation from Ru/sup II/, and even more for the Os/sup II/ species, into the ..pi..* ligand orbitals. With the conjugated 1,3-butadiene ligand, the inner hydrogen H/sub c/ of the uncoordinated olefinic unit, adjacent to the coordinated olefin, is also shielded by 0.78 ppM for the Ru/sup II/ complex and 0.98 ppM for the Os/sup II/ complex. The binuclear 1,3-butadiene-bridged complexes A/sub 5/Ru(1,3-butadiene)RuA/sub 5//sup 4 +/, A/sub 5/Os(1,3-butadiene)OsA/sub 5//sup 4 +/, and A/sub 5/Os(1,3-butadiene)RuA/sub 5//sup 4 +/ (A = NH/sub 3/ or ND/sub 3/) have been prepared. The mixed-metal (Os/sup II/, Ru/sup II/) ion's /sup 1/H shifts are observed upfield of the (Ru/sup II/, Ru/sup II/) binuclear ion and downfield of the (Os/sup II/, Os/sup II/) analogue. The /sup 1/H resonance positions in the binuclear ions are further upfield of the related mononuclear A/sub 5/Ru(1,3-butadiene)/sup 2 +/ and A/sub 5/Os(1,3-butadiene)/sup 2 +/ complexes. 19 references, 8 figures, 4 tables.
- Research Organization:
- Univ. of Pittsburgh, PA (USA)
- OSTI ID:
- 6260132
- Journal Information:
- Inorg. Chem.; (United States), Vol. 27:19
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMINES
CHEMICAL PREPARATION
DIENES
OSMIUM COMPLEXES
RUTHENIUM COMPLEXES
CARBON 13
EXPERIMENTAL DATA
NMR SPECTRA
PROTONS
BARYONS
CARBON ISOTOPES
COMPLEXES
DATA
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
FERMIONS
HADRONS
HYDROCARBONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUCLEONS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation