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Investigations into Phosphinoamide-Supported Heterobimetallic Complexes of Niobium and Tantalum
Başlık:
Investigations into Phosphinoamide-Supported Heterobimetallic Complexes of Niobium and Tantalum
Yazar:
Culcu, Gursu, author.
ISBN:
9780438051805
Yazar Ek Girişi:
Fiziksel Tanımlama:
1 electronic resource (279 pages)
Genel Not:
Source: Dissertation Abstracts International, Volume: 79-10(E), Section: B.
Advisors: Christine M. Thomas Committee members: Theodore Betley; Bruce M. Foxman; Barry Snider; Christine M. Thomas.
Özet:
The primary goal of this project is to investigate the metal-metal interactions in heterobimetallic complexes of niobium. First, in order to stabilize a reduced niobium center, different synthetic routes had to be developed. Then, a series of Nb/M (M = Fe, Co, Ni, Cu) dihalide complexes were synthesized and fully characterized. Structural parameters and theoretical investigations show that single and multiple bonding is possible between Nb and late metals such as Fe, Co and Ni, as well as dative interactions between Nb and Cu. This study is aimed to have a better understanding of Nb-metal interactions in order to find the suitable pair of metals to pursue bond activation and catalysis. For example, the NbIV/FeI pair was selected to synthesize a reduced complex that is isoelectronic with the complex Co( iPr2PNMes)3Zr(THF) (Zr/Co). The synthesized reduced complex Nb(iPrNPPh2) 3Fe-PMe3 has a polar covalent Nb-Fe triple bond with an extremely short metal-metal bond length. The solid state structure reveals the shortest Nb-M distance characterized by X-ray crystallography. The initial reactivity studies of the complex shows significant difference compared to its Zr/Co analog. For example the Nb(iPrNPPh2)3Fe-PMe3 complex only shows two-electron redox chemistry towards aryl and alkyl azides while the Zr/Co complex can undergo a four electron oxidation in the presence of these reagents. It is concluded that the PMe3 ligand inhibits the reactivity possible with Nb( iPrNPPh2)3Fe-PMe3.
A heterobimetallic complex of tantalum was also synthesized and characterized using a bis(phosphinoamide)-ligated tantalum precursor. Crystallographic and spectroscopic characterization of the Ta/Ni complex (PhCCPh)Ta( iPrNPPh2)2(mu2-I)Ni-I suggests a TaV-NiI core.
Notlar:
School code: 0021
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Yer Numarası | Demirbaş Numarası | Shelf Location | Lokasyon / Statüsü / İade Tarihi |
---|---|---|---|
XX(680000.1) | 680000-1001 | Proquest E-Tez Koleksiyonu | Arıyor... |
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