The chemistry of transition metal clusters has been a fast developing area of organometallic research in recent years. Compared to mononuclear metal complexes, polynuclear clusters offer more opportunities to study cooperative effects and electron reservoir properties between contiguous metal centers, in addition to functioning as storehouses for the release of catalytically active small fragments capable of exhibiting heterosite subtrate activation. Theoretically, metal clusters are intermediates between mononuclear complexes and metal surfaces, i.e., they serve as a bridge between molecular and solid-state chemistry. Transition metal clusters are ideal candidates to study M-M interactions stretching from the single bond to the collective metallic behavior found in a three-dimensional network of metal atoms. The reaction between the redox-active diphoshpine ligand bpcd and RU(CO) has been examined under a variety of conditions. The disubstituted cluster Ru3(CO)10(bpcd)(2) has been synthesized and shown to contain a chealating bpcd ligand, on the basis of IR and 31P NMR data. The cluster 2 (chelating isomer) undergoes cluster fragmentation at ambient temperatures in the dark to give the binuclear compound 3 and Ru3(CO)12, with no evidence for the formation of 4. Both 3 and 4 have been isolated and fully characterized in solution by IR and NMR spectroscopy, and the solid-state structure of each new binuclear compound has been established by X-ray diffraction analysis. Independent experiments reveal that dinuclear 3 is converted to 4 by 366 nm light with a quantum efficiency of .0364.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc935834 |
| Date | 05 1900 |
| Creators | Shen, Huafeng |
| Contributors | Richmond, Michael G., Schwartz, Martin, Bott, Simon G., Acree, William E. (William Eugene) |
| Publisher | University of North Texas |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | xv, 169 leaves : ill., Text |
| Rights | Public, Shen, Huafeng, Copyright, Copyright is held by the author, unless otherwise noted. All rights |
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