Sites of Reactivity During Ligand-Exchange Reactions in Octahedral Group VIB Metal Carbonyls Page: 2
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Asali, Khali1 Jamil, Sites of Reactivity During
Ligand-Exchange Reactions in Octahedral Group VIB Metal
Carbonyls. Doctor of Philosophy (Chemistry), December,
1979, 135 pp., 15 tables, 31 illustrations, bibliography, 118
The site of initial metal-carbonyl bond-breaking
during ligand-exchange reactions in a series of octahedral
metal carbonyls of the type (I^JMtCO)^ (M = Cr, Mo, W;
L2 = diphos, phen, dipy) has been determined employing
infrared spectroscopy and Fourier transform nuclear magnetic
resonance spectroscopy. The results of this study reveal,
for all metal carbonyl complexes of the type mentioned
above, that loss of CO occurs exclusively at an axial
position (cis to the bidentate ligand, I^)•
The dynamic nature of the five-coordinate intermediates,
such as (diphos)Mo(CO)^/ (phen)M(CO)^ (M = Cr, Mo, W),
and (dipy)Cr(CO)3, which are generated in solution upon CO
dissociation, is reported and discussed. The results of
this investigation confirm that these intermediates are
fluxional on the time scale of CO-exchange process. A
mechanism which describes the site of initial metal-carbonyl
bond-breaking and the fluxionality of the five-coordinate
intermediate during ligand-exchange reactions in the
complexes (L~)M(CO). is proposed.
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Asali, Khalil Jamil. Sites of Reactivity During Ligand-Exchange Reactions in Octahedral Group VIB Metal Carbonyls, dissertation, December 1979; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc330718/m1/2/: accessed June 20, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .