Jump to main content
Jump to site search

Issue 24, 2016
Previous Article Next Article

Structure and bonding of group 4-nickel heterobimetallics supported by 2-(diphenylphosphino)pyrrolide ligands

Author affiliations

Abstract

The synthesis of a full series of group 4/nickel complexes supported by a 2-(diphenylphosphino)pyrrolide (NP) ligand is reported. Treatment of the homoleptic, 8-coordinate M(NP)4 monometallic precursors with Ni(COD)2 (COD = 1,5-cyclooctadiene) yielded the heterobimetallic complexes (κ2-NP)M(μ2-NP)3Ni (M = Ti, Zr, Hf). Although X-ray crystallographic analysis reveals similarly short metal–metal distances in all three complexes, quantum chemical calculations indicate that ZrNi (5) and HfNi (6) contain only single Ni → M dative bonds while TiNi (4) has an additional Ti–Ni π-bond. All three complexes have quasireversible reductions by cyclic voltammetry, and 1-electron chemical reduction of 4 by Na(Hg) yields the anion, [Na][(κ2-NP)Ti(μ2-NP)3Ni] (7). X-ray and computational analysis indicate that the 1-electron reduction of 4 completely breaks the metal–metal bond, yielding a formally TiIII–Ni0 complex. Ti–Ni bonding can also be disrupted by coordination of CO, wherein Ni → CO backbonding effectively outcompetes Ni → Ti dative bonding.

Graphical abstract: Structure and bonding of group 4-nickel heterobimetallics supported by 2-(diphenylphosphino)pyrrolide ligands

Back to tab navigation

Supplementary files

Publication details

The article was received on 31 jan. 2016, accepted on 25 feb. 2016 and first published on 01 mar. 2016


Article type: Paper
DOI: 10.1039/C6DT00431H
Citation: Dalton Trans., 2016,45, 9892-9901
  •   Request permissions

    Structure and bonding of group 4-nickel heterobimetallics supported by 2-(diphenylphosphino)pyrrolide ligands

    P. L. Dunn, R. K. Carlson, L. Gagliardi and I. A. Tonks, Dalton Trans., 2016, 45, 9892
    DOI: 10.1039/C6DT00431H

Search articles by author

Spotlight

Advertisements