Photochemically induced transformations of transition complexes

Technical Report · Mon May 17 00:00:00 EDT 1993

OSTI ID:5649270

Brown, J E

Photolysis of the dinuclear complex ((n5-C5H5)Fe(CO)2)2 in CHCl3 results in the formation of (n5-c5H5)Fe(CO)2Cl through intermediate 17-electron radicals of the form (n5-C5H5)Fe(CO)2. The photolyses of the related diphosphine-bridged compounds ((n5-C5H5)Fe(CO)2-u-DPPX, where DPPX=DPPM, DPPE and DPPP and therefore are (Ph2P)2CH2, (Ph2P)2C2H, and (Ph2P)2C3H6 respectively), are described. The synthesis and photolysis of the analogous ruthenium DPPM dimer is also described. In contrast to the behavior of the simple iron dinuclear species, the DPPM and DPPE phosphine bridged compounds undergo photolysis in CHCl3 to yield products containing formyl substituted cyclopentadienyl rings. Details of the reactions studied and product characterizations using multinuclear NMR, IR and single crystal X-ray diffraction techniques are described. A possible mechanism for the formation of the formyl derivatives 5 is outlined. In the synthesis and purification of ((n5C5H5)Ru(CO))2-u-DPPM and the attempted synthesis of the ((n5-C5H5)Ru(CO))2-u-DPPE, two ruthenium monomers of the form (n5-C5H5)Ru(Cl)DPPX resulted. A possible reaction pathway for the synthesis of these two monomers as byproducts in the ruthenium phosphine dimer preparation is suggested. Full structural and spectral characterizations of the monomeric compounds are Included. Photosynthesis, Organometallics, Reimer-Tiemann.

• Research Organization: Naval Academy, Annapolis, MD (United States)
• OSTI ID: 5649270
• Report Number(s): AD-A-271112/5/XAB; USNA-TSPR-200
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANOMETALLIC COMPOUNDS
CHEMICAL PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
PHOTOLYSIS
CHEMICAL REACTIONS
IRON COMPLEXES
MONOMERS
PHOSPHINES
PHOTOSYNTHESIS
PURIFICATION
RADICALS
RUTHENIUM COMPLEXES
COMPLEXES
DECOMPOSITION
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
SYNTHESIS
400500* - Photochemistry