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  • Open Daily: 10am - 10pm
    Alley-side Pickup: 10am - 7pm

    3038 Hennepin Ave Minneapolis, MN
    612-822-4611

Open Daily: 10am - 10pm | Alley-side Pickup: 10am - 7pm
3038 Hennepin Ave Minneapolis, MN
612-822-4611
Synthesis and Reactivity of Rhodium and Iridium Silyl and Silylene Complexes Supported by Pnp Pincer Ligands.

Synthesis and Reactivity of Rhodium and Iridium Silyl and Silylene Complexes Supported by Pnp Pincer Ligands.

Calimano, Elisa E.

Paperback

Chemistry

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ISBN10: 1243771984
ISBN13: 9781243771988
Publisher: Proquest Umi Dissertation Pub
Pages: 274
Weight: 1.09
Height: 0.58 Width: 7.44 Depth: 9.69
Language: English
Chapter 1. Oxidative addition of bulky primary, secondary and tertiary silanes to PNP (PNP = [N(2-PiPr2-4-Me-C 6H3)2]-) iridium complexes (PNP)IrH2 and (PNP)Ir(COE) (10) afforded iridium silyl hydride complexes (PNP)Ir(H)(SiRR'R) (1-7). Addition of 2 equiv of PhSiH3 or (3,5-Me2C6H3)SiH 3 to (PNP)IrH2 or 10 yielded disilyl complexes (PNP)Ir(SiH2R)2 (R = Ph (8) and 3,5-Me 2C6H3 (9)). Hydride abstraction from (PNP)Ir(H)(SiH2R) (R = Mes (1), Trip (4), Dmp (5)) by [Ph3C][B(C6F5) 4] afforded iridium silylene complexes I(PNP)(H)Ir=SiR(H)1IB(C6F5)41 (R = Mes (11), Trip (12), Dmp (13)) exhibiting downfield 29Si NMR resonances (247 ppm (11 ), 234 ppm (12), 226 ppm (13)) and downfield 1H NMR resonances for the Si-H group (10.65 ppm (11) 10.76 ppm (12), 9.76 ppm (13)). Chapter 2. Hydrogen-substituted silylene complex [(PNP)(H)Ir=SiMes(H)][B(C 6F5)4] (1) reacts rapidly with 1-hexene, styrene, cis-cyclooctene, vinyltrimethylsilane and p-chlorostyrene at ambient temperature to afford disubstituted silylene complexes [(PNP)(H)Ir=SiMes(R)][B(C6F5)4] (R = (CH2)5CH3 (3), CH 2CH2Ph (4), C8H15 ( 5), (CH2CH2)SiMe3 (6) and (CH2CH2)C6H4Cl (7)), respectively, via Si-C bond formation. Complex 1 and [(PNP)(H)Ir=SiPh 2][B(C6F5)4] (2) are catalysts for alkene hydrosilation of primary silanes with a high degree of anti-Markovnikov selectivity. Addition of H3SiMes to complex 1 afforded [P2N(SiH(Mes)(Hex))IrH(SiH2Mes)][B(C6F 5)4] (8) featuring a beta-agostic interaction demonstrated by a JSiH of 102 Hz for the N-Si H hydrogen. Chapter 3. Reactions of PNP-supported silylene complexes [(PNP)(H)Ir=SiRR'][B(C6F5)4] (R = R' = Ph (1) and, R = H, R' = Mes (2)) with Lewis bases, carbonyl compounds, alcohols and amines were investigated. Addition of DMAP (4-dimethylaminopyridene) to 1 and 2 produced base-stabilized silylene complexes [(PNP)(H)IrSiRR'(DMAP)][B(C6F5) 4] (R = R' = Ph (3) and, R = H, R' = Mes (4)). Reactions of 2 with benzophenone and benzaldehyde afforded the products of stoichiometric hydrosilation, the heteroatom-substituted silylene complexes [(PNP)(H)Ir=SiMes(OCH(Ph)(R))][B(C6F5) 4] (R = Ph (5) and, R = H (6)). Complex 1 reacted with DMF or benzophenone, and 2 reacted with DMF to afford base-stabilized silylene complexes of the type [(PNP)(H)IrSiRR'(B)][B(C 6F5)4] (R = H, R' = Mes, B = DMF (7); R = R' = Ph, B = DMF (8) and O=CPh2 (9)). In contrast, treatment of 1 with acetophenone afforded {(PNPH)IrH[SiPh 2(OC(=CH2)Ph)]}[B(C6F5)4] (10), from activation of the C-H bond at the a-carbon position of acetophenone. Chapter 4. New rhodium and iridium complexes supported by the phenyl-substituted PNP pincer ligand PNPPhH (HN(2-PPh 2-4-Me-C6H3)2) (1) were synthesized. The reaction of 2 equiv of 1 with [(COD)IrCl] 2 afforded the coordination complex [(PNPPhH)Ir(COD)]Cl (2) featuring hydrogen bonding between the N-H group and the chloride anion, as characterized by NMR spectroscopy and X-ray crystallography. Reaction of 1 with [(COE)2IrCl]2 or [(COE) 2RhCl]2 in benzene provided a mixture of complexes including (PNPPhH)MHCl2 (M = Ir (4), M = Rh ( 7)) and (PNP)M(COE) (M = Ir (5), M = Rh (8)). (Abstract shortened by UMI.)

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