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Pentaammineruthenium(II) and pentaammineosmium(II) complexes of olefins and linear dienes related to 1,3-butadiene

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00292a016· OSTI ID:6260132
;
(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), Journal Name: Inorg. Chem.; (United States) Vol. 27:19; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AMINES
BARYONS
CARBON 13
CARBON ISOTOPES
CHEMICAL PREPARATION
COMPLEXES
DATA
DIENES
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FERMIONS
HADRONS
HYDROCARBONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NMR SPECTRA
NUCLEI
NUCLEONS
NUMERICAL DATA
ORGANIC COMPOUNDS
OSMIUM COMPLEXES
POLYENES
PROTONS
RUTHENIUM COMPLEXES
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES