Brammell, Christina 1987- (2012-12). Organometallic Chemistry Supported by the PNP Pincer Framework for Both Early and Late Transition Metals. Master's Thesis. Thesis uri icon

abstract

  • Tridentate "pincer" ligands provide a unique balance of stability and reactivity in organometallic chemistry. The development of diarylamido-based PNP pincer ligands has led to many applications in catalysis, including the potential to facilitate unique chemical transformations at transition metal centers. The main objective of this thesis was to explore transition metal chemistry supported by the PNP pincer framework for both early and late transition metals. In Chapter I, the history behind the design and synthesis of pincer complexes is described. The advantages and disadvantages of various pincer ligands are reviewed to show the reasoning behind the synthesis of the PNP pincer framework. Chapter II discusses the synthesis of novel Hf and Ta complexes involving the PNP ligand. Reactions of (PNP)HfCl3 with large alkyl Grignards led to double alkylation and triple alkylation was achieved with methyl Grignard. (PNP)HfMe3 and (PNP)Hf(CH2SiMe3)2Cl displayed remarkably irregular coordination environments about hafnium, in contrast to the approximately octahedral structure of (PNP)HfCl3. (PNP)HfMe3 was found to be thermally stable at 75 degrees C, whereas thermolysis of (PNP)Hf(CH2SiMe3)2Cl under similar conditions led to a mixture of products. The major decomposition product is believed to be a Hf alkylidene complex on the basis of in situ NMR spectroscopic observations (e.g., delta 248.2 ppm in the 13C{1H} NMR spectrum). The reaction of (PNP)TaF4 with an excess of ethyl Grignard led primarily to the double alkylation product, (PNP)Ta(CH2CH3)2F2. Repeating this reaction in the presence of excess ethyl Grignard and dioxane resulted in the formation of an ethylene complex, (PNP)Ta(=CHCH3)(C2H4). In Chapter III, a C-C reductive elimination study is described comparing two pincer ligand scaffolds: Me(PNP) ligand and TH(PNP) ligand. The tied ligand has previously been found to be more sterically demanding than the untied ligand, which has allowed for faster N-C cleavage, faster oxidative addition and a more selective alkyne dimerization catalyst. This study reveals that the tied ligand complex, TH(PNP)Rh(C6H4CF3)(Ph), undergoes slower reductive elimination of p-Ph-C6H4CF3 (< 4% after 7 h at 38 degrees C; t1/2 = 7.7 h at 64 degrees C; t1/2 = 2.13 h at 75 degrees C) than Me(PNP)Rh(C6H4CF3)(Ph) (t1/2 = 15.6 min at 38 degrees C).
  • Tridentate "pincer" ligands provide a unique balance of stability and reactivity in organometallic chemistry. The development of diarylamido-based PNP pincer ligands has led to many applications in catalysis, including the potential to facilitate unique chemical transformations at transition metal centers. The main objective of this thesis was to explore transition metal chemistry supported by the PNP pincer framework for both early and late transition metals. In Chapter I, the history behind the design and synthesis of pincer complexes is described. The advantages and disadvantages of various pincer ligands are reviewed to show the reasoning behind the synthesis of the PNP pincer framework.

    Chapter II discusses the synthesis of novel Hf and Ta complexes involving the PNP ligand. Reactions of (PNP)HfCl3 with large alkyl Grignards led to double alkylation and triple alkylation was achieved with methyl Grignard. (PNP)HfMe3 and (PNP)Hf(CH2SiMe3)2Cl displayed remarkably irregular coordination environments about hafnium, in contrast to the approximately octahedral structure of (PNP)HfCl3. (PNP)HfMe3 was found to be thermally stable at 75 degrees C, whereas thermolysis of (PNP)Hf(CH2SiMe3)2Cl under similar conditions led to a mixture of products. The major decomposition product is believed to be a Hf alkylidene complex on the basis of in situ NMR spectroscopic observations (e.g., delta 248.2 ppm in the 13C{1H} NMR spectrum). The reaction of (PNP)TaF4 with an excess of ethyl Grignard led primarily to the double alkylation product, (PNP)Ta(CH2CH3)2F2. Repeating this reaction in the presence of excess ethyl Grignard and dioxane resulted in the formation of an ethylene complex, (PNP)Ta(=CHCH3)(C2H4).

    In Chapter III, a C-C reductive elimination study is described comparing two pincer ligand scaffolds: Me(PNP) ligand and TH(PNP) ligand. The tied ligand has previously been found to be more sterically demanding than the untied ligand, which has allowed for faster N-C cleavage, faster oxidative addition and a more selective alkyne dimerization catalyst. This study reveals that the tied ligand complex, TH(PNP)Rh(C6H4CF3)(Ph), undergoes slower reductive elimination of p-Ph-C6H4CF3 (< 4% after 7 h at 38 degrees C; t1/2 = 7.7 h at 64 degrees C; t1/2 = 2.13 h at 75 degrees C) than Me(PNP)Rh(C6H4CF3)(Ph) (t1/2 = 15.6 min at 38 degrees C).

publication date

  • December 2012