dc.creator | Chmely, Stephen Christopher | |
dc.date.accessioned | 2020-08-22T20:39:49Z | |
dc.date.available | 2010-08-11 | |
dc.date.issued | 2010-08-11 | |
dc.identifier.uri | https://etd.library.vanderbilt.edu/etd-07302010-110908 | |
dc.identifier.uri | http://hdl.handle.net/1803/13736 | |
dc.description.abstract | The effects of adding steric bulk to the ligands of main group organometallic complexes are examined in this dissertation. First, bulky allyl complexes of beryllium and magnesium, using the 1,3-bis(trimethylsilyl)allyl ligand, are explored, which results in the first structurally authenticated allyl complex of beryllium as well as the first structurally authenticated π-allyl complex of magnesium. In addition, spectroscopic and DFT investigations of these and related complexes are presented.
In addition, it was determined that a commonly used preparation of Ca[N(SiMe3)2]2 involving the reaction of potassium bis(trimethylsilyl)amide with CaI2 can produce material that contains substantial amounts of potassium, probably in the form of a calciate such as K[Ca{N(SiMe3)2}3]. This possibility was confirmed with density functional theory calculations and the potassium calciate was synthesized and structurally authenticated. Discussion of the 1H NMR spectrum of deliberately doped solutions of Ca[N(SiMe3)2]2 with potassium bis(trimethylsilyl)amide is presented in detail.
Furthermore, treatment of the phosphonium salt [Me(t-Bu)P(C5Me4H)2]I with 2 equiv of KH produces the coordination polymer {K[Me(t-Bu)P(C5Me4)2](thf)}∞. If the phosphonium salt reacts with a single equivalent of KH followed by Ca[N(SiMe3)2]2, the calcium complex [Me(t-Bu)P(C5Me4)2]CaN(SiMe3)2 is produced, which is structurally related to Cp′2LnX organolanthanides. Density functional theory studies of the H3E (E = C, Si, P)-substituted cyclopentadienyl ring indicate that the energy required for out-of-plane bending of the substituent decreases in the order H3C > H3Si > H3P. Preliminary work towards the synthesis of an allyl-containing phosphonium-bridged ansa complex is also presented.
Finally, arsenic and antimony triiodide react with three equiv of Na[C5Me4H] in THF to form the yellow tris(tetramethylcyclopentadienyl) derivatives M(C5Me4H)3. When equimolar amounts of SbI3 and Na[C5Me4H] react in THF, the orange diiodo species Sb(C5Me4H)I2 is produced. The effect on the complexes of the methylated cyclopentadienyl rings varies from minimal to substantial. A single crystal X-ray structure of M(C5Me4H)3 reveals three σ-bound rings with strongly localized bonding. The diiodo complex displays an η3-bound ring and forms a coordination polymer in the solid state, with ordering driven by intermolecular I…I´ and Me…Me´ van der Waals attractions. Spectroscopic and DFT investigations of the compounds are also presented. | |
dc.format.mimetype | application/pdf | |
dc.subject | organometallic | |
dc.subject | chemistry | |
dc.subject | beryllium | |
dc.subject | magnesium | |
dc.subject | inorganic | |
dc.title | Sterically demanding ligands and their effect on the structure and reactivity of main group metal complexes | |
dc.type | dissertation | |
dc.contributor.committeeMember | Eva Harth | |
dc.contributor.committeeMember | David Wright | |
dc.contributor.committeeMember | Charles Lukehart | |
dc.contributor.committeeMember | Bridget Rogers | |
dc.type.material | text | |
thesis.degree.name | PHD | |
thesis.degree.level | dissertation | |
thesis.degree.discipline | Chemistry | |
thesis.degree.grantor | Vanderbilt University | |
local.embargo.terms | 2010-08-11 | |
local.embargo.lift | 2010-08-11 | |
dc.contributor.committeeChair | Timothy P. Hanusa | |