The structural definition of adducts of stoichiometry MX:dppx (1:1) M = Cu I , Ag I , X = simple anion, dppx=Ph 2 P(CH 2 ) x PPh 2 , x = 3–6 Effendy a,b , Corrado Di Nicola c , Mauro Fianchini c , Claudio Pettinari c, * , Brian W. Skelton b , Neil Somers b , Allan H. White b a Jurusan Kimia, FMIPA Universitas Negeri Malang, Jalan Surabaya 6, Malang, 65145, Indonesia b Chemistry M313, The University of Western Australia, Crawley, W. A. 6009, Australia c Dipartimento di Scienze Chimiche, Universita ` degli Studi di Camerino, via S. Agostino 1, 62032 Camerino MC, Italy Received 23 August 2004; accepted 22 September 2004 Abstract Single crystal X-ray structural characterizations are recorded for a wide range of adducts of the form MX:dppx (1:1) (n) , M = sil- ver(I) (predominantly), copper(I), X = simple (pseudo-) halide or oxy-anion (the latter spanning, where accessible, perchlorate, nitrate, carboxylate – a range of increasing basicity), dppx=bis(diphenylphosphino)alkane, Ph 2 P(CH 2 ) x PPh 2 , x = 3–6. Adducts are defined of two binuclear forms: (i) [LM(l-X) 2 L], with each ligand chelating a single metal atom, and (ii) [M(l-X) 2 (l-(P- L-P 0 )) 2 M 0 ] where both ligands L and halides bridge the two metal atoms; a few adducts are defined as polymers, the ligands connecting M(l-X) 2 M 0 kernels, this motif persisting in all forms. Synthetic procedures for all adducts have been reported. All com- pounds have been characterized both in solution ( 1 H, 13 C, 31 P NMR, ESI MS) and in the solid state (IR). Ó 2004 Elsevier B.V. All rights reserved. Keywords: Silver; 31 P NMR; ESI; X-ray crystal structure; Diphosphine 1. Introduction In preceding papers [1–3], in pursuit of our goal of achieving the definition of adducts of simple salts of the univalent group 11 metals copper and silver, MX, with symmetrical simple bis(diphenylpnicogeno)alkane ligands, Ph 2 E(CH 2 ) x EPh 2 , E = P (predominantly), As, ÔdpexÕ, we have described studies of adducts of the form MX:dpex (1:1) (n) for the simplest ligands ÔdppmÕ and, less extensively, ÔdpamÕ (E = P, As; x = 1). ÔdppeÕ (E = P; x = 2) is also a widely used ligand, but our studies of its complexation of MX has shown it to yield, predomi- nantly, adducts of stoichiometry MX:dppe (2:3) [4], while adducts of the higher homologues, ÔdpppÕ, ÔdppbÕ, ÔdppnÕ, ÔdpphÕ, (E = P only, x = 3–6), readily yield once more a wide array of adducts of 1:1 stoichiometry. Again, at this stage of our studies, our results pertain pre- dominantly to M = Ag, E = P systems, augmented by a number of copper(I) counterparts. Again we point out that we have found the latter more difficult of access, and, further, that the acquisition of material of useful form for the X-ray studies is sometimes not compatible with the production of analytically pure bulk samples. We further note the aggregation of this body of work over a considerable period of time, employing in some circumstances ÔsolventsÕ (such as pyridine (ÔpyÕ), 2- methylpyridine (ÔmpyÕ)) which may seem unusual – in a number of cases, these were initially consequent on at- tempts to produce mixed nitrogen/phosphine ligand ad- ducts, wherein the nitrogen ligand, unlike its more usual behaviour with unidentate phosphine ligand com- plexes, did not coordinate, but, nevertheless, provided 0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2004.09.047 * Corresponding author. Tel.: +39 0737 402234; fax: +39 0737 637345. E-mail address: Claudio.pettinari@unicam.it (C. Pettinari). www.elsevier.com/locate/ica Inorganica Chimica Acta 358 (2005) 763–795