| Autor: |
Macaulay CM; Department of Chemistry, Dalhousie University, 6274 Coburg Road, P.O. 15000, Halifax, Nova Scotia B3H 4R2, Canada., Samolia M; Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, USA., Ferguson MJ; X-Ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada., Sydora OL; Research and Technology, Chevron Phillips Chemical Company LP, 1862 Kingwood Drive, Kingwood, Texas 77339, USA., Ess DH; Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, USA., Stradiotto M; Department of Chemistry, Dalhousie University, 6274 Coburg Road, P.O. 15000, Halifax, Nova Scotia B3H 4R2, Canada., Turculet L; Department of Chemistry, Dalhousie University, 6274 Coburg Road, P.O. 15000, Halifax, Nova Scotia B3H 4R2, Canada. |
| Abstrakt: |
Treatment of (PN)NiX (X = NHdipp or OtBu; PN = N-phosphinoamidinate ligand) with Me2PhSiH in benzene solvent afforded the crystallographically characterized, antifacial-coordinated, dinuclear species 1, the formation of which corresponds to the hitherto unknown net Ni-H addition of two equivalents of the putative (PN)NiH intermediate across C[double bond, length as m-dash]C units within a single benzene molecule. Computational analysis supports the view of 1 as being comprised of two cationic (PN)NiII fragments ligated by a substituted butadiene dianion μ2-η3:η3-C6H82- bridging group. Also described is the formation and characterization of three-coordinate (PN)Ni(alkyl) complexes stabilized by β-agostic (alkyl = Et, 2; n-Bu, 3; n-hexyl, 4) or γ-agostic (alkyl = neopentyl, 5) interactions, and our efforts to employ 2 and 3 as synthons for the generation of (PN)NiHvia β-hydride elimination. Notably, compound 5 represents both the first crystallographically characterized three-coordinate Ni-alkyl complex featuring a heterobidentate ligation, and the first neutral γ-agostic NiII-alkyl complex. |
