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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
Part I: Bonding Properties and Reactivity of the Metal-Boron Bond in Metal Borane Compounds. Part II: Homogeneous Hydrodesulfu

Part I: Bonding Properties and Reactivity of the Metal-Boron Bond in Metal Borane Compounds. Part II: Homogeneous Hydrodesulfu

Pang, Keliang

Paperback

Chemistry

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ISBN10: 1243578610
ISBN13: 9781243578617
Publisher: Proquest Umi Dissertation Pub
Pages: 190
Weight: 0.77
Height: 0.40 Width: 7.44 Depth: 9.69
Language: English
In chapter 1, two palladaboratrane compounds, namely {[mu-kappa 1, kappa3-B( mimBut )3]Pd}2 and [kappa4-B( mimBut )3]Pd(PMe3), as well as a sandwich compound featuring an interesting boron-functionalized Tm ligand, namely [kappa 2-AcOB( mimBut )3]2Pd, have been isolated and structurally characterized. Molecular orbital analysis was employed to investigate the bonding properties of the metal-to-boron dative bond in [kappa4-B( mimBut )3]Pd(PMe3) and a previously reported ditantalum compound featuring a bridging BH3 group, namely Ta2(mu-BH 3)(mu-dmpm)3(kappa2-BH4) 2. The results lead to a general conclusion that coordination of a Z type ligand to a single metal center reduces its dn number by 2 to dn-2, while coordination of a Z type ligand to a metal-metal bond formally reduces the metal-metal bond order by 1. In chapter 2, evidence is presented to confirm the transformation of [T TmBut ]MCl to [kappa4-B( mimBut )3]MCl (M = Ni, Co). Synthesis of a relevant complex, [kappa 3-H, S, S- TmBut ]CoCl(py), is also achieved. [kappa3-H, S, S - TmBut ]CoCl(py) features a 3-center-2-electron B-H-Co interaction and its formation suggests that the proposed B-H activation in [ TmBut ]CoCl to form [kappa4-B( mimBut )3]CoCl is metal promoted. Reactions of the nickelaboratrane [kappa 4-B( mimBut )3]NiCl result in the formation of various products, which include [kappa4-B( mimBut )3]NiX (X = OAc, NCS, N3), [Y TmBut ]NiZ (Y=F, Z=Cl; Y=Cl, Z=Cl, Br, I; Y= NCS, N3, Z=I) and (4,0)-(mu-N, S- mimBut )4Ni2. A palladium paddlewheel compound, namely (4,0)-(mu-N, S- mimBut )4Pd2 has also been isolated from reaction of the corresponding palladaboratrane [kappa4-B( mimBut )3]Pd(PMe3). In addition, two nickel compounds featuring a unique [S4N] coordination mode about the metal center have been synthesized, namely {[F TmBut ]NiNCS}2 and [F TmBut ]Ni(kappa2-N, S- mimBut ). Chapter 3 reports the synthesis and reactivity of two group V polyhydride complexes, namely Ta(PMe3)4H5 and Nb(BH 4)(PMe3)4H2. They both exhibit diverse reactivity which lead to the formation of various interesting products, such as Ta(C2H5)(C2H4)2(PMe 3)2 featuring Ta-C-C-H beta-agostic interaction, Ta(eta 5-C6H5CHCH2Ph)2(PMe 3)3H2 featuring an eta5-cyclohexadienyl ligand, Ta(eta2- PzBut2 )2(PMe3)2H3 featuring hydride ligands that have very downfield NMR chemical shift and Nb2(p-BH 4)2(CO)4(PMe3)4 featuring two bridging BH4 groups. Moreover, both Ta(PMe3) 4H5 and Nb(BH4)(PMe3)4H 2 show HDS activity toward benzo[b]thiophene and are able to abstract sulfur from benzo[b]thiophene and release the corresponding hydrocarbon-ethylbenzene, indicating that they are potential platforms for HDS studies and hopeful precursors of homogenous HDS catalysts.

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