Reactivity of Lewis Acids with Coordinated Ligands of Late Transition Metal Complexes

• Main Author: Boone, Michael Patrick
• Other Authors: Stephan, Douglas
• Language: en_ca
• Published: 2013
• Subjects: Chemistry; Inorganic Chemistry; Frustrated Lewis Pairs; Organometallic Chemistry; 0488
• Online Access: http://hdl.handle.net/1807/43487

With hundreds of papers published since 2006 on frustrated Lewis pair (FLP) chemistry the development of innovative Lewis acids and Lewis bases is a quickly expanding field. This thesis is separated into two parts. The first part investigates the incorporation of tridentate ligands on ruthenium alkylidene species and their subsequent reactivity with Lewis acids and FLPs in an attempt to synthesize innovative olefin metathesis catalysts. The second part explores the use of ligands coordinated to ruthenium metal centers as a method for expanding the Lewis acid and base functionalities in the field of FLP chemistry. Ruthenium-alkylidene complexes of the general formula ((PEP-Cy)RuX2(CHPh) (E = O, NH, NMe; X = Cl, Br)) were obtained via the reaction of Grubbs 1st generation catalysts with the tridentate ancillary ligands O(CH2CH2PCy2)2 [POP-Cy], HN(CH2CH2PCy2)2 [PN(H)P-Cy] and MeN(CH2CH2PCy2)2 [PN(Me)P-Cy]. Subsequent treatment of GaX3 with these alkylidene species resulted in the formation of cationic alkylidyne-hydride complexes, ([(PEP Cy)Ru(H)(X)(CPh)][GaX4] where E = O, NH, NMe; X = Cl, Br; however, when E = NH, a mixture of alkylidyne-hydride and cationic alkylidene species was observed. Conversely, when E = NMe, alkylidyne-hydride formation was followed by transfer of the alkylidene fragment to the Me of the ligand framework. Subsequently, Ru-acetylide complexes [LRu(PPh3)2CCPh] were reacted with the B(C6F5)3 to afford the para-attacked products [LRu(PPh3)2C=C(Ph)((C6F4)B(F)(C6F5)2)] (L = Cp, Indenyl). Further studies revealed that [IndRu(PPh3)2CCPh] and ER3 (E = B, R = C6F4H; E = Al, R = C6F5) formed FLP mixtures that effected the activation of CO2 between the nucleophilic β-acetylide carbon and the Lewis acid to form [IndRu(PPh3)2C=C(Ph)C(O)O-ER3] or [IndRu(PPh3)2C=C(Ph)C(O ER3)2] when E = Al and R = C6F5. Similarly, these FLP combinations were used to activate phenylacetylene and benzaldehyde forming the species [IndRu(PPh3)2C=C(Ph)C(Ph)=C(H)(ER3)] and [IndRu(PPh3)2C=C(Ph)C(Ph)O-ER3], respectively. Lastly, the synthesis of [((Ph2PC6H4)2BCl)(η6-Ph))RuCl] was achieved via the reaction of (Ph2PC6H4)2BPh with (Ph3P)RuCl2. Subsequent halide abstraction with K[B(C6F5)4] resulted in the formation of [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] which was used as a carbon-based Lewis acid in adduct formation with Lewis bases to yield products of the general form [((Ph2PC6H4)2B)(η5 C6H5 o-LB))RuCl][B(C6F5)4] (LB = PPh3, PCy3, PMe3, SIMes, etc). The activation of H2 was also achieved when combinations of [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] and bulky phosphines were employed, resulting in the products [((Ph2PC6H4)2B)(η5 C6H6))RuCl][B(C6F5)4], [((Ph2PC6H4)2B)(η6 C6H5))RuCl][B(C6F5)4] and [R3PH][B(C6F5)4] (R = Mes, tBu, Cy). Similarly, [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] was used to catalytically hydrogenate sterically encumbered aldimines at room temperature with catalyst loadings as low as 1 mol% via a FLP-type mechanism.