Synthesis, spectroscopic and structural characterisation of copper, silver and gold complexes of the mixed P/O-donor ligand Ph2P(CH2)2O(CH2)2O(CH2)2PPh2

Heuer, Bjorn, Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711 and Reid, Gillian 2000. Synthesis, spectroscopic and structural characterisation of copper, silver and gold complexes of the mixed P/O-donor ligand Ph2P(CH2)2O(CH2)2O(CH2)2PPh2. Polyhedron 19 (7) , pp. 743-749. 10.1016/S0277-5387(00)00291-6

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Abstract

Reaction of L1 (L1=Ph2P(CH2)2O(CH2)2O(CH2)2PPh2) with [Cu(MeCN)4]PF6 or AgBF4 in CH2Cl2 solution yields the complexes [Cu(L1)]PF6 and [Ag(L1)]BF4 respectively as white solids. Spectroscopic measurements are consistent with coordination via the P-donors and the crystal structure of [Ag(L1)]BF4 confirms that L1 acts as a trans-chelate giving an unusual example of approximately linear P2-coordination at Ag(I) (∠P–Ag–P=164.66(4)°) and, despite the availability and proximity of the ether O atoms, these remain essentially uncoordinated (Ag⋯O=2.95 Å), thus reflecting the low affinity of the soft Ag(I) ion for hard O-donor ligands. [AuCl(tht)], L1 and TlPF6 react in a 1:1:1 molar ratio in MeCN solution to yield the analogous Au(I) species [Au(L1)]PF6, the structure of which also shows linear P2-coordination and once again the O-donors are non-coordinating, at a distance of ca. 3.16 Å from Au(I). The neutral dinuclear species [(AuCl)2(L1)] is readily formed by reaction of [AuCl(tht)] with L1 in a 2:1 molar ratio in MeCN. Confirmation of the coordinated Cl ligands comes from IR spectroscopy, ν(Au–Cl)=324 cm−1, and δ(31P) which is indicative of a PCl donor set at Au(I). This arrangement is confirmed in the solid state from the crystal structure. The related phosphathia complex [(AuBr)2(L2)] (L2=Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2) is prepared similarly from [AuBr(tht)] and L2 in MeCN solution and its structure reveals the AuBr units each coordinated to one P-donor and directed to the same side as the o-C6H4 unit.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Uncontrolled Keywords:	Copper complexes; Silver complexes; Gold complexes
Publisher:	Elsevier
ISSN:	0277-5387
Last Modified:	21 Oct 2022 10:53
URI:	https://orca.cardiff.ac.uk/id/eprint/41650

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