Transition Metal Polypnictides from Zintl Ions
| dc.contributor.advisor | Eichhorn, Bryan W. | |
| dc.contributor.author | Charles, Scott | |
| dc.contributor.department | Chemistry & Biochemistry | |
| dc.contributor.publisher | Digital Repository at the University of Maryland | |
| dc.contributor.publisher | University of Maryland (College Park, Md) | |
| dc.date.accessioned | 2019-08-23T13:31:57Z | |
| dc.date.available | 2019-08-23T13:31:57Z | |
| dc.date.issued | 1995 | |
| dc.description.abstract | The chemistry of the soluble E7 3- ions (E = P, As, Sb) with various transition metal complexes has been investigated. Alloys of K3E7 react with (arene)M(CO)3 (M = Cr, Mo, W) complexes in the presence of three equivalents of 2,2,2-crypt in ethylenediamine to give [K(2,2,2-crypt)]3[E7M(CO)3] complexes. Nine [E7M(CO)3] 3- compounds (E = P, As, Sb; M = Cr, Mo, W) have been prepared. The compounds have norbomadiene-like E7 fragments, with a formal negative charge associated with the unique two-coordinate pnictogen furthest from the transition metal. The bonding is described as E7 π-type interactions with the metal center. 31p NMR studies show that these compounds undergo an intramolecular wagging process in solution. The [E7M(C0)3] 3- ions are modestly basic and highly nucleophilic. The complexes react with weak acids, tetraalkylammonium salts and (arene)M'(CO)3 complexes to form the [K(2,2,2-crypt)]2[HE7M(CO)3], [K(2,2,2- crypt)]2[RE7M(CO)3] and [K(2,2,2-crypt)]3[(L2)(CO)3M'E7M(CO)3] compounds, respectively. Each of the structures contains a norbornadiene-like E7 fragment bound η4 to the M(CO)3 fragment and η1 to the appended moiety [H+, R+, M(CO)3(en)] that is attached to the pnictogen atom furthest from the M(CO)3 center. The [K(2,2,2-crypt)]3 [η4-E7M(CO)3] complexes also react with carbon monoxide at the M(CO)3 center and reversible binds CO to form [K(2,2,2-crypt)]3[η4-E7M(CO)4] complexes. These complexes are more easily protonated and undergo faster alkylations of the E7 cages than the parent [K(2,2,2-crypt)]3[η4-E7M(CO)3] compounds. Each of these structures contains an E7 fragment bound η2 to the M(C0)4 center. Products were characterized by various physical and spectroscopic techniques including UV-vis, IR, 1H, 13C, and 31P NMR spectroscopies, mass spectrometry, elemental analyses, and single crystal X-ray diffraction studies. | en_US |
| dc.identifier | https://doi.org/10.13016/59cv-elgh | |
| dc.identifier.other | ILLiad # 1258797 | |
| dc.identifier.uri | http://hdl.handle.net/1903/24721 | |
| dc.language.iso | en | en_US |
| dc.title | Transition Metal Polypnictides from Zintl Ions | en_US |
| dc.type | Dissertation | en_US |