Issue 21, 2004
From the journal:

Dalton Transactions

The structural characteristics of organozinc complexes incorporating N,N′-bidentate ligands†

Samuel J. Birch,a   Sally R. Boss,a   Sarah C. Cole,b   Martyn P. Coles,*b   Robert Haigh,a   Peter B. Hitchcockb  and  Andrew E. H. Wheatley*a  

* Corresponding authors

a Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK
E-mail: aehw2@cam.ac.uk
Fax: +44 (0)1223 336362
Tel: +44 (0)1223 763122

b Department of Chemistry, University of Sussex, Falmer, Brighton, UK
E-mail: m.p.coles@sussex.ac.uk
Fax: +44 (0)1273 677196
Tel: +44 (0)1273 877339

Abstract

Dimethylzinc reacts with an excess of N-2-pyridylaniline 6 to give the homoleptic species, Zn[PhN(2-C5H4N)]28. Single crystal X-ray diffraction reveals a solid-state dimer based on an 8-membered (NCNZn)2 core motif. Zn[CyN(2-C5H4N)]Me (Cy = c-C6H11) 10, prepared by the combination of ZnMe2 with the corresponding cyclohexyl-substituted pyridylamine, is also dimeric in the solid state but reveals a central (ZnN)2 metallacycle. Employment of (p-Tol)NH(2-C5H4N) (p-Tol = 4-MeC6H4) 11 yielded the tris(zinc) adduct Zn3[(p-Tol)N(2-C5H4N)]4Me212, which incorporates a central chiral molecule of ‘Zn[(p-Tol)N(2-C5H4N)]2’ 12a, that bridges two ‘Zn[(p-Tol)N(2-C5H4N)]Me’ 12b units. A similar trimetallic structure is noted when the pyridylaniline substrate 11 is replaced with the bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH), affording Zn3(hpp)4Me213. Spectroscopic studies point to retention of the solid-state structure of 13 in hydrocarbon solution. Reaction of 13 with dimesityl borinic acid, Mes2BOH (Mes = mesityl), affords Zn3(hpp)4(OBMes2)214 in which the trimetallic core is retained. This reactivity is in contrast to the closely related reaction of dimeric Zn[Me2NC{NiPr}2]Me 15 with Mes2BOH, which yielded Zn[Me2NC{NiPr}2][OBMes2]·Me2NC{NiPr}{NHiPr} 16 as a result of protonation at the guanidine ligand in addition to the Zn–Me bond.

Graphical abstract: The structural characteristics of organozinc complexes incorporating N,N′-bidentate ligands

About
Cited by
Related
Download options Please wait...

Article information

DOI
https://doi.org/10.1039/B410945G
Article type
Paper
Submitted
19 Jul 2004
Accepted
09 Sep 2004
First published
27 Sep 2004

Dalton Trans., 2004, 3568-3574

Permissions

Request permissions

The structural characteristics of organozinc complexes incorporating N,N′-bidentate ligands

S. J. Birch, S. R. Boss, S. C. Cole, M. P. Coles, R. Haigh, P. B. Hitchcock and A. E. H. Wheatley, Dalton Trans., 2004, 3568 DOI: 10.1039/B410945G

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