Synthesis and thermal isomerization of carbonyl and nitrosyl amine-phosphine complexes of ruthenium(II)

Journal Article · Sun May 01 04:00:00 EDT 1988 · Sov. J. Coordinat. Chem.; (United States)

OSTI ID:7190904

Nikol'skii, A B; Popov, A M; Repinskaya, T S; Kukushkin, Yu N; Egorova, M B

New mixed-ligand chelates with the formula (Ru(bipy)(PP)YX)/sup n+/ (bipy stands for 2,2'-bipyridyl; PP stands for 1,2-bis(diphenylphosphino)ethane and cis-1,2,-bis-(diphenylphosphino)ethylene; Y = CO (n = 1), NO (n = 2); X = Cl, Br, I) have been synthesized. The compounds have been obtained in the form of the two possible isomers with cis structures. It has been shown that the isomers of the complexes containing a CO or NO ligand in the trans position to a phosphorus atom of the diphosphine are thermally unstable, and at elevated temperatures they undergo exothermic cis-cis isomerization with migration of the ligand with a multiple bond to the transposition to a bipyridyl nitrogen atom in the solid phase. A process of thermal decarbonylation has been discovered in solutions of the carbonyl complexes with a CO ligand in a trans position to the phosphine, and the occurrence of reversible bonding of carbon monoxide by the complexes cis-(Ru(bipy)(PP)X/sub 2/) has been established. The complexes have been characterized by data from elemental analysis, IR and /sup 31/P NMR spectroscopy, and cyclic voltammetry. It has been shown that the chelating phosphine increases the electrophilic activity of the /RuCO//sup 2 +/ fragment to a considerable extent and lowers the reductive stability of the /RuNO//sup 3 +/ fragment.

• Research Organization: A. A. Zhdanov Leningrad State Univ. (USSR)
• OSTI ID: 7190904
• Journal Information: Sov. J. Coordinat. Chem.; (United States), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 13:7; ISSN SJCCD
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMINES
CARBONYLS
CHELATES
CHEMICAL REACTIONS
COMPLEXES
HYDROGEN 1
HYDROGEN ISOTOPES
INFRARED SPECTRA
ISOMERIZATION
ISOMERS
ISOTOPES
LIGANDS
LIGHT NUCLEI
NITROSO COMPOUNDS
NMR SPECTRA
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
REDOX POTENTIAL
RUTHENIUM COMPLEXES
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TEMPERATURE EFFECTS
TRANSITION ELEMENT COMPLEXES