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Structural Diversity in the Coordination of Amidines and Guanidines to Monovalent Metal Halides

journal contribution
posted on 2023-06-08, 06:42 authored by Sarah H Oakley, Delia B Soria, Martyn P Coles, Peter B Hitchcock
A series of structurally characterised, monovalent metal-halide complexes incorporating neutral amidine and guanidine ligands is reported. N,N-diphenylbenzamidine reacted with copper(I) chloride to afford the bis-ligand complex [CuCl(PhC{NPh}{NHPh})2]2(1), that exists as a chlorine bridged dimer in the solid state, with a non-symmetrical distribution of NHCl interactions within the Cu2Cl2 metallacycle. In contrast, only one equivalent of the guanidine, Me2NC{NiPr}{NHiPr}(2), is coordinated in the copper(I) iodide complex [CuI(Me2NC{NiPr}{NHiPr})]2(3), which was also isolated as the dimer with bridging halide atoms. The molecular structure of the bicyclic guanidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH), is reported, revealing a hydrogen bridged dimer with extensive delocalisation throughout the ligand framework. Coordination of hppH to lithium chloride afforded the dimeric bis-ligand complex [LiCl(hppH)2]2(4) in which each hppH molecule interacts with a different chlorine atom of the central Li2Cl2 core of the molecule via NHCl hydrogen bonding. In contrast the 2 1 ligand to metal complex is formed with silver(I) chloride to afford AgCl(hppH)2(5), a unique example of a monomeric, three-coordinate silver chloride supported by nitrogen-based ligands. The series of mixed ligand complexes [CuX(hppH)(PPh3)]n(6, X = Cl, n= 1; 7, X = Br, n= 2; 8 X = I, n= 2) have also been synthesised and structurally characterised, allowing comparisons of the relative coordinating behaviour of hppH and PPh3 as neutral donors at copper(I) centres to be made.

History

Publication status

  • Published

Journal

Dalton Transactions

ISSN

1477-9226

Publisher

RSC Publishing

Issue

4

Volume

-

Page range

537 - 546

Department affiliated with

  • Chemistry Publications

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

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