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Oligo-nuclear Silver Thiocyanate Complexes With Monodentate Tertiary Phosphine Ligands, Including Novel 'Cubane' and 'Step' Tetramer Forms of AgSCN : PR3 (1:1)4

Oligo-nuclear Silver Thiocyanate Complexes With Monodentate Tertiary Phosphine Ligands, Including Novel 'Cubane' and 'Step' Tetramer Forms of AgSCN : PR3 (1:1)4

Graham A Bowmaker, Corrado Di Nicola, Effendy, John V Hanna, Peter C Healy, Scott P King, Fabio Marchetti, Claudio Pettinari, Ward T Robinson, Brian W Skelton, Alexandre N Sobolev, Aurel Tăbăcaru, Allan H White

Dalton Trans. 2013 Jan 7;42(1):277-91.

PMID: 23114624

Abstract:

Adducts of a number of tertiary pnicogen ligands ER(3) (triphenyl-phosphine and -arsine (PPh(3),AsPh(3)), diphenyl,2-pyridylphosphine (PPh(2)py), tris(4-fluorophenyl)phosphine (P(C(6)H(4)-4F)(3)), tris(2-tolyl)phosphine (P(o-tol)(3)), tris(cyclohexyl)phosphine (PCy(3))), with silver(I) thiocyanate, AgSCN are structurally and spectroscopically characterized. The 1:3 AgSCN : ER(3) complexes structurally defined (for PPh(3),AsPh(3) (diversely solvated)) take the form [(R(3)E)(3)AgX], the thiocyanate X = NCS being N-bound, thus [(Ph(3)E)Ag(NCS)]. A 1:2 complex with PPh(2)py, takes the binuclear form [(pyPh(2)P)(2)Ag()Ag(PPh(2)py)(2)] with an eight-membered cyclic core. 1:1 complexes are defined with PPh(2)py, P(o-tol)(3) and PCy(3); binuclear forms [(R(3)P)Ag()Ag(PR(3))] are obtained with P(o-tol)(3) (two polymorphs), while novel isomeric tetranuclear forms, which may be envisaged as dimers of dimers, are obtained with PPh(2)py, and, as further polymorphs, with PCy(3); these latter may be considered as extensions of the 'cubane' and 'step' forms previously described for [(R(3)E)AgX](4) (X = halide) complexes. Solvent-assisted mechanochemical or solvent-assisted solid-state synthesis methods were employed in some cases, where complexes could not be obtained by conventional solution methods, or where such methods yielded a mixture of polymorphs unsuitable for solid-state spectroscopy. The wavenumbers of the ν(CN) bands in the IR spectra are in broad agreement with the empirical rule that distinguishes bridging from terminal bonding, but exceptions occur for compounds that have a double SCN bridged dimeric structure, and replacement of PPh(3) with PPh(2)py apparently causes a significant decrease in ν(CN) to well below the range expected for bridging SCN in these structures. (31)P CP MAS NMR spectra yield additional parameters that allow a correlation between the structures and spectra.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP1701935	Silver thiocyanate		1701-93-5	Price

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