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Chemistry of Rh/sub 2/(CO)/sub 2/(Cl)/sub 2/(dppm)/sub 2/ and compounds derived therefrom: Structural characterization of Rh/sub 2/(CO)Cl/sub 4/(dppm)/sub 2/ and (Rh/sub 2/(CO)Cl/sub 3/(dppm)/sub 2/MeOH)(PF/sub 6/)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00297a007· OSTI ID:5762053
; ;
Rh/sub 2/(CO)/sub 2/Cl/sub 2/(dppm)/sub 2/ (dppm = (Ph/sub 2/P)/sub 2/CH/sub 2/) reacts with 1 equiv of PhICl/sub 2/ in a dilute CH/sub 2/Cl solution to yield Rh/sub 2/(CO)/sub 2/Cl/sub 4/ (dppm)/sub 2/ (1), which was characterized in solution by ir and /sup 31/P(/sup 1/H) NMR spectroscopies. Rh/sub 2/(CO)/sub 2/Cl/sub 4/(dppm)/sub 2/ slowly decarbonylates in solution or more rapidly in the presence of an additional 1 equiv of PhICl/sub 2/, to give Rh/sub 2/(CO)Cl/sub 4/(dppm)/sub 2/ (2), which was characterized by x-ray crystallography. Crystal structure of 2 is reported. The reaction of 2 with CO gives back Rh/sub 2/(CO)/sub 2/Cl/sub 4/(dppm)/sub 2/ wile with 1 equiv of PhICl/sub 2/ it yields Rh/sub 2/Cl/sub 6/(dppm)/sub 2/ (3). Compound 2 further reacts with 1 equiv of AgPF/sub 6/ to give (Rh/sub 2/(CO)Cl/sub 3/(dppm)/sub 2/MeOH)(PF/sub 6/) (4), which was characterized by ir (solution and solid) and /sup 31/P(/sup 1/H) NMR spectroscopies and by x-ray crystallography, and the crystal structure of 4 is reported. The CO ligand may be removed from 2 with Me/sub 3/NO to give Rh/sub 2/Cl/sub 4/(dppm)/sub 2/ (5), a previously reported compound in which the dppm ligands are in a cisoid arrangement about the metal atoms. Conversely, Rh/sub 2/Cl/sub 4/(dppm)/sub 2/ reacts with CO under pressure to yield 2. Direct chlorination of 5 to give 3 has not been accomplished. 17 refs., 4 figs., 5 tabs.
Research Organization:
Texas A M Univ., College Station (USA)
OSTI ID:
5762053
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:24; 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
AROMATICS
BARYONS
CARBONYLS
CHEMICAL PREPARATION
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
CRYSTAL STRUCTURE
DATA
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
FLUORIDES
FLUORINE COMPOUNDS
HADRONS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NMR SPECTRA
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS FLUORIDES
PHOSPHORUS ISOTOPES
PROTONS
RUTHENIUM COMPLEXES
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES