Spectroscopic and structural studies on 1[hair space]:[hair space]2 adducts of silver(I) salts with tricyclohexylarsine

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Graham A. Bowmaker, Effendy , Brian W. Skelton, Allan H. White , Brian W. Skelton and Allan H. White


Abstract

A series of mononuclear complexes [Ag{As(C6H11)3}2X] (X = Cl, Br, I, CN, NCO, OClO3, O2NO or O2CCF3) have been synthesized and characterised by room temperature single crystal X-ray determinations and low-frequency vibrational spectroscopy. For X = Cl, Br, I or OClO3 the crystal structures are isomorphous with a number of their previously recorded P(C6H11)3 counterparts, crystallising in the familiar monoclinic C[hair space][hair space]2/c array with the Ag–X bond lying on a crystallographic 2 axis (the perchlorate is disordered) which also relates the pair of As(C6H11)3 ligands. The silver environment in all is planar three-co-ordinate XAgAs2. For X = CN, NCO or O2NO the derivative lower-symmetry triclinic P[1 with combining macron] array, also common among the P(C6H11)3 analogues is found. The trifluoroacetate, resembling the nitrate in that the anion behaves as a small ‘bite’ bidentate ligand, [Ag{As(C6H11)3}2(O2CCF3)], is monoclinic space group P21/n. The thiocyanate by contrast, utilising the ambidentate capacity of the SCN ligand, remarkably, is a linear polymer, · · ·[hair space][hair space]{As(C6H11)3}2Ag(SCN)Ag(SCN)[hair space][hair space]· · ·, triclinic, space group P1, in which the silver atom environment is four-co-ordinate, NSAgAs2. Far-IR spectra of the halide and pseudo-halide complexes in the series exhibit single bands due to ν(AgX) vibrational modes at 230, 165, 139, 262 and 311 cm–1 for X = Cl, Br, I, NCO and CN respectively. These are all higher than the values for the corresponding P(C6H11)3 complexes, suggesting that the Ag–X bonding is stronger in the As(C6H11)3 complexes, this being the result of weakened Ag–L bonding in going from L = P(C6H11)3 to As(C6H11)3.


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