Issue 24, 2016

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

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

Supplementary files

Article information

Article type
Paper
Submitted
31 Janv. 2016
Accepted
25 Febr. 2016
First published
01 Marts 2016

Dalton Trans., 2016,45, 9892-9901

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements