Spectroscopic and structural studies on 1 : 1 adducts of silver(I) salts with tricyclohexylphosphine

Abstract

The 1 : 1 adducts of silver( 1) halides (AgX; X = C1, Br or I) with tricyclohexylphosphine have been prepared and their room-temperature single-crystal structures, solid-state cross polarization magic angle spinning (CP MAS) 3 1 P NMR, solution 31P NMR and far-IR spectra determined. The solid-state structures of the chloride and bromide complexes recrystallized from pyridine arc unsolvated, isomorphous, centrosymmetric dihalidebridged dimers, [.(AgX[P(C,H 1)3] ,I, with three-co-ordinate metal centres. Crystals are triclinic, space group

catena-Poly[[di-μ-chloro-bis[(triphenylphosphine)silver(I)]]-μ-2-aminopyrimidine-κ2N1:N3]

“…The AgÐP distance is slightly shorter in (I) than in [AgCl(PPh 3 ) 2 ] 2 , (III) (2.469 A Ê ; Cassel, 1979) or [AgXP-(C 6 H 11 ) 3 ] 2 (X is Cl, Br or I; Bowmaker et al, 1996). The AgÐ Cl distances in (I) agree with those in (III) (2.669 A Ê ).…”

Coordination complexes of silver(I) with tertiary phosphine and related ligands

“…Thus, the trialkylphosphine PEt 3 yields tetrameric cubane clusters [AgX(PEt 3 )] 4 (X = Cl − , Br − [13] and I − [14]) and the reaction of equimolar ratios of PPh 2 Bu with silver(I) halides yields tetrameric cubane structures of type [AgX(PPh 2 Bu)] 4 (X = Cl − , Br − and I − ) [15]. However, the isolation and characterisation of cubane -[AgI(PPh 3 )] 4 [12,16] from CHCl 3 /Et 2 O and the step analogue from CH 2 Cl 2 /Et 2 O [11,17], as well as the isolation of the sterically unfavoured cubane complexes [AgI(PCy 3 )] 4 (Cy = cyclohexyl) [18], [CuI(PPh 3 )] 4 [19] and [CuBr(P t Bu 3 )] 4 [20], shows that the nature of the determining factors are not clearly understood. Other factors, such as solvent of crystallisation, may be important determinants of the formation of either cubane, 1, or step, 2, structures.…”

“…Surprisingly, the PCy 3 [18] and AsCy 3 [23] adducts of AgX (X = Cl − , Br − ) show dimerisation, using the halides as bridging ligands, whereas the AgI adduct is a cubane tetramer. Addition of pyridine to this tetramer resulted in the formation of dimeric [{AgI(PCy 3 )} 2 Py] with bridging iodides and an unusual bridging pyridine in a 'crevice' co-ordination mode, weakly co-ordinated to both silver atoms [18] (Table 1). [48].…”

Photoluminescent Metal-Sulfur Clusters Derived from Tetrathiometalates: Metal-to-Metal Charge-Transfer Excited States of d0-d10 Heterobimetallic Sulfido Clusters with Bulky Phosphine Ligands

“…[29] [Cu 2 (dcpm) 2 (MeCN) 2 ](ClO 4 ) 2 was prepared by the literature method. [26] Ag(PCy 3 )ClO 4 and Au(PCy 3 )Cl were prepared from the reactions of PCy 3 with AgClO 4 and K[AuCl 4 ] (all purchased from Aldrich), respectively, by a similar preparation to that of Ag(PCy 3 )Cl [30] and Au(PPh 3 )Cl, respectively. [31] 1 H and 31 P NMR spectra were recorded on Bruker DPX 300 and DRX 500 FT-NMR spectrometers.…”