Intermolecular influences on M-M multiple bonds from thin-film UPS studies of group VI M/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ complexes

Journal Article · Wed May 27 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00245a046· OSTI ID:6510446

Lichtenberger, D L; Kristofzski, J G

Dimetal tetracarboxylate complexes have provided a rich arena for study of metal-metal bonding since the presence of sigma-, ..pi..-, and delta-orbital symmetry interactions was first explained in 1964. The title compounds have proven particularly fruitful for investigating these interactions because the volatility of these compounds makes them suitable for gas-phase photoelectron studies, thus allowing detailed experimental examination of the theoretical principles of bonding. Development of the basic bonding description for these complexes has been accompanied by numerous studies of the effects of bridging ligands and axial interactions on the metal-metal bond strength and bond length. As one step to examining the electronic effects of axial occupation on the metal-metal bond, they have obtained the photoelectron spectra of thin films of anhydrous group VI tetraacetates. In these thin films the axial positions of the metal-metal bonds are occupied by neighboring molecules. With appropriate preparation of these films in ultrahigh vacuum conditions, they are able to obtain spectra which exhibit only slight broadening as compared to the gas-phase spectra, indicating that each molecule contributing to the observation is in a similar electronic environment. The axial positions of the metal-metal bonds are most likely occupied by the oxygen atoms of the neighboring complexes, as found in the single-crystal structures.

• Research Organization: Univ. of Arizona, Tucson
• OSTI ID: 6510446
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 109:11
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETATES
CHEMICAL BONDS
MOLYBDENUM COMPLEXES
TUNGSTEN COMPLEXES
EXPERIMENTAL DATA
PHOTOELECTRON SPECTROSCOPY
THIN FILMS
CARBOXYLIC ACID SALTS
COMPLEXES
DATA
ELECTRON SPECTROSCOPY
FILMS
INFORMATION
NUMERICAL DATA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties