Heterometallic Cuboidal Clusters M 3 M′Q 4 (M ) Mo, W; M′) Sn, Pb, As, Sb; Q ) S, Se): From Coordination Compounds to Supramolecular Adducts Rita Herna ´ ndez-Molina,* ,† Irina V. Kalinina, ‡ Pavel A. Abramov, ‡ Maxim N. Sokolov, ‡ Alexandr V. Virovets, ‡ Javier G. Platas, § Rosa Llusar, § Victor Polo, § Cristian Vicent, § and Vladimir P. Fedin ‡ Departamento de Quı ´mica Inorga ´ nica, UniVersidad de La Laguna, 38200 La Laguna, Tenerife, Islas Canarias, Spain, NikolaeV Institute of Inorganic Chemistry, Prospect LaVrentyeVa 3, 630090 NoVosibirsk, Russia, and Departament de Quı ´mica Fı ´sica i Analı ´tica, UniVersitat Jaume I, AVda. Sos Baynat s/n, E-12071 Castello ´ , Spain Received August 8, 2007 Reactions of the incomplete cuboidal clusters [M 3 Q 4 (acac) 3 (py) 3 ] + (M ) Mo, W; Q ) S, Se) with group 14 and 15 metal complexes with the s 2 p 0 electronic configuration (AsPh 3 , SbPh 3 , SbCl 3 , SbI 3 , PbI 3 - , SnCl 3 - ) led to heterometal incorporation with the formation of cuboidal clusters of the type [M 3 (EX 3 )Q 4 (acac) 3 (py) 3 ] n+ (n ) 0 for Sn, Pb; n ) 1 for As, Sb), whose structures were determined by X-ray diffraction. The cuboidal clusters can be described as complexes of the cluster tridentate ligand [M 3 Q 4 (acac) 3 (py) 3 ] + (µ 2 -chalcogen atoms as donors) with the EX 3 , where the E atom attains a distorted octahedral coordination. Analysis based on the bond distances E-Q gives the following sequence of affinity: As < Sb; Pb < Sn ≈ Sb; SbPh 3 < SbI 3 ≈ SbCl 3 ;W 3 S 4 <W 3 Se 4 . Interaction energies at the gas phase between [W 3 Q 4 (acac) 3 (py) 3 ] + (Q ) S, Se) and SbX 3 (X ) I, Ph) were computed at the DFT level (BP86/TZP). The magnitude of the interaction depends strongly on the substituents at Sb, and the replacement of iodine by the phenyl group decreases the interaction energy from -9.21 to -2.70 kcal/mol and from -12.73 to -3.85 kcal/mol for the W 3 SbS 4 and W 3 SbSe 4 cores, respectively. Introduction Triangular chalcogenide-bridged clusters of Mo and W, M 3 (µ 3 -Q)(µ 2 -Q) 3 4+ (Q ) S, Se), have a unique ability to incorporate post-transition metals of 12-15 groups in low and intermediate oxidation states (electronic configura- tions s 2 ), to form cuboidal clusters of the M 3 M′(µ 3 -Q) 4 (4 + n)+ type, 1 first reported by Lu in 1987 2 (M′ ) Ga, In, n ) 1; Ge, Sn, Pb, n ) 2; As, Sb, Bi, n ) 3). Other examples followed suit. 3 Though this incorporation does not lead to bonding between M and M′ (M‚‚‚M′ distances are quite long, 3.8-4.0 Å), it stabilizes the M 3 cluster framework, as evidenced from shortening of the M-M bonds. At least in the case of Sn(II), calculations and physical measure- ments indicate a charge transfer from Sn to M (Mo or W), which can be, perhaps oversimplistically, described in terms of Sn(II) f Sn(IV) oxidation. 3b The situation is less clear-cut for other metals because, for example, Pb(II) or Sb(III) are not easy oxidized. Most of the synthetic work was done on the sulfide clusters, and very little is known about their selenide analogues. An additional point of interest is added by possible applications due to interesting nonlinear optic properties of some of these compounds. 4 In this work, we report reactions of the incomplete cuboidal clusters [M 3 Q 4 (acac) 3 (py) 3 ] + (M ) Mo, W; Q ) S, Se) and their dmpe and NCS derivatives with group 14 and 15 metal compounds having an s 2 p 0 electronic configuration and substituents of different electronegativity at the metal (AsPh 3 , SbPh 3 , SbCl 3 , SbI 3 , PbI 3 - , SnCl 3 - ), together with their structural characterization and quantum chemical studies. * To whom correspondence should be addressed. E-mail: caesar@ che.nsk.su. † Universidad de La Laguna. ‡ Nikolaev Institute of Inorganic Chemistry. § Universitat Jaume I. (1) Hernandez-Molina, R.; Sokolov, M. N.; Sykes, A. G. Acc. Chem. Res. 2001, 34, 223. (2) (a) Lu, S.-F.; Huang, J.-Q.; Lin, Y.-H.; Huang, J.-L. Acta Chim. Sinica 1987, 3, 191. (b) Yu, R.-M. (b) Lu, S.-F.; Huang, J.-Q.; Huang, X.- Y.; Wu, Q.-J.; Wu, D.-X. Inorg. Chem. 2000, 39, 5348. Inorg. Chem. 2008, 47, 306-314 306 Inorganic Chemistry, Vol. 47, No. 1, 2008 10.1021/ic701581u CCC: $40.75 © 2008 American Chemical Society Published on Web 12/11/2007