Issue 33, 2008
From the journal:

Dalton Transactions

Insertion reactions of β-diketiminate-stabilised calcium amides with 1,3-dialkylcarbodiimides†‡

Anthony G. M. Barrett,*b   Mark R. Crimmin,b   Michael S. Hill,*a   Peter B. Hitchcockc  and  Panayiotis A. Procopioud  

* Corresponding authors

a Department of Chemistry, University of Bath, Claverton Down, Bath, UK
E-mail: m.s.hill@bath.ac.uk

b Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London, UK

c The Chemistry Laboratory, University of Sussex, Falmer, Brighton, East Sussex, UK

d GlaxoSmithKline Medicines Research Centre, Gunnels Wood Road, Stevenage, Hertfordshire, UK

Abstract

A series of heteroleptic β-diketiminate-stabilised calcium amides of the form [{ArNC(Me)CHC(Me)NAr}Ca{NR1R2}(THF)] (Ar = 2,6-diisopropylphenyl; R1 = H, R2 = Ar; R1 = H, R2 = CH2CH2OMe; R1 = R2 = Ph) react with 1,3-dialkylcarbodiimides, R3N[double bond, length as m-dash]C[double bond, length as m-dash]NR3 (R3 = Cy, iPr), to yield the corresponding insertion products [{ArNC(Me)CHC(Me)NAr}Ca{(R3N)2CNR1R2}(THF)] at room temperature in hydrocarbon solutions. These latter compounds contain both β-diketiminate and guanidinate ligands bound to calcium. Solid-state data are consistent with the guanidinate ligands adopting a number of binding modes including κ2 through κ3 coordination, with varying degrees of delocalisation of the non-bound guanidinate nitrogen lone-pair across the π-framework of the ligand. DFT computational studies have been conducted to address these variations in coordination behaviour.

Graphical abstract: Insertion reactions of β-diketiminate-stabilised calcium amides with 1,3-dialkylcarbodiimides

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Article information

DOI
https://doi.org/10.1039/B717383K
Article type
Paper
Submitted
09 Nov 2007
Accepted
10 Jan 2008
First published
11 Jul 2008

Dalton Trans., 2008, 4474-4481

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Insertion reactions of β-diketiminate-stabilised calcium amides with 1,3-dialkylcarbodiimides

A. G. M. Barrett, M. R. Crimmin, M. S. Hill, P. B. Hitchcock and P. A. Procopiou, Dalton Trans., 2008, 4474 DOI: 10.1039/B717383K

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