284476-01-3Relevant academic research and scientific papers
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,Reid, Gillian
, p. 743 - 749 (2000)
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) (angleP-Ag-P = 164.66 (4)°) and, despite the availability and proximity of the ether O atoms, these remain essentially uncoordinated (Ag···O = 2.95 A?), thus reflecting the low affinity of the soft Ag (I) ion for hard O-donor ligands. [ AuCl (tht) ], L1 and TIPF6 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 A?. 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)2L2)] (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. (C) 2000 Elsevier Science Ltd.
