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The hexanuclear cluster {Pt(6)}H(2) (2) contains a sterically hindered and chemically stable {Pt(6)} = Pt(6)(mu-PtBu(2))(4)(CO)(4) core, with the six metals forming an edge-bridged tetrahedron. The two hydrides are the reactive sites of the cluster and lie on opposite sides of the cluster, terminally bonded to the two "apical" edge-bridging platinum centres. Indeed, cluster 2 reacts with acids of different acidity (HA = CF(3)SO(3)H, HBF(4), p-CH(3)-C(6)H(4)-SO(3)H, CF(3)COOH, PhCOOH and CH(3)COOH), affording, after evolution of two equivalents of dihydrogen, the corresponding anion-substituted clusters {Pt(6)}A(2) (4). We suggest that the reaction proceeds through a mechanism similar to the one generally accepted for the analogous protonation of mononuclear hydrides, with some of the intermediates partially characterised at low temperature. Interestingly, the reverse reaction, the heterolytic splitting of H(2) by clusters 4, occurs readily under mild conditions. The anions in clusters 4a and 4b (4a: A = CF(3)SO(3), 4b: A = BF(4)) are bonded in the solid state but very easily dissociate in solution and may be substituted under mild conditions by weak ligands, such as CH(2)Cl(2) or CH(3)CN. With dialkyl ethers, the reaction proceeds further with the heterolytic splitting of a C-H bond of the ethereal ligand. This process allowed us to isolate the polymer [{Pt(6)}(CH(2)OCH(2)CH(2)OCH(2))](x) (8), in which the {Pt(6)} cluster units are connected by insulating spacers arising from dimethoxyethane. The results of single-crystal X-ray diffraction studies on 4a and 8 are also reported.

Pulsed gradient spin-echo (PGSE) diffusion characteristics for a) the new [brucinium][X] salts 6 a-f [a: X = BF(4)(-); b: X = PF(6)(-); c: X = MeSO(3)(-), d: X = CF(3)SO(3)(-); e: X = BArF(-); f: X = PtCl(3)(C(2)H(4))(-)], b) 4-tert-butyl-N-benzyl analogue, 7 and c) the aryl carbocations (p-R-C(6)H(4))(2)CH 9 a (R = CH(3)O) and 9 b (R = (CH(3))(2)N), (p-CH(3)O-C(6)H(4))(x)CPh(3-x)(+) 10 a-c (x = 1-3, respectively) and (p-R-C(6)H(4))(3)C(+) 11 (R = (CH(3))(2)N) and 12 (R = H) all in several different solvents, are reported. The solvent dependence suggests strong ion pairing in CDCl(3), intermediate ion pairing in CD(2)Cl(2) and little ion pairing in [D(6)]acetone. (1)H, (19)F HOESY NMR spectra (HOESY: heteronuclear Overhauser effect spectroscopy) for 6 and 7 reveal a specific approach of the anion with respect to the brucinium cation plus subtle changes, which are related to the anion itself. Further, for carbocations 9-12, (all as BF(4)(-) salts) based on the NOE results, one finds marked changes in the relative positions of the BF(4)(-) anion. In these aryl cationic species the anion can be located either a) very close to the carbonium ion carbon b) in an intermediate position or c) proximate to the N or O atom of the p-substituent and remote from the formally positive C atom. This represents the first example of such a positional dependence of an anion on the structure of the carbocation. DFT calculations support the experimental HOESY results. The solid-state structures for 6 c and the novel Zeise's salt derivative, [brucinium][PtCl(3)(C(2)H(4))], 6 f, are reported. Analysis of (195)Pt NMR and other NMR measurements suggest that the eta(2)-C(2)H(4) bonding to the platinum centre in 6 f is very similar to that found in K[PtCl(3)(C(2)H(4))]. Field dependent T(1) measurements on [brucinium][PtCl(3)(C(2)H(4))] and K[PtCl(3)(C(2)H(4))], are reported and suggested to be useful in recognizing aggregation effects.

PGSE diffusion, 19F, 1H HOESY and 13C NMR studies for a series of [Ru(Cp*)(eta6-arene)][PF6] (1) salts are presented. The solid-state structure of [Ru(Cp*)(eta6-fluorobenzene)][PF6] (1 c) is reported. The extent of the ion pairing and the relative positions of the ions are shown to depend on the arene. For the solvent dichloromethane, new and literature PGSE data for PF6(-) salts of transition-metal, inorganic, and organic salts are compared. Taken together, these new results show that the charge distribution and the ability of the anion to approach the positively charged positions (steric effects due to molecular shape) are the determining factors in deciding the amount of ion pairing. DFT calculations of the charges in four salts of type 1, as well as in a variety of other salts, using a natural population analysis (NPA), support this view. This represents the first attempt, using experimental data, to understand, correlate, and partially explain the various degrees of ion pairing in a widely different collection of salts.

The tridentate dianionic ligand 2-[2'-(hydroxyisopropoxyphosphoryl)phenylsulfanyl]benzoate (L(2-)) reacts with cis-[Pt(NH(3))(2)(H(2)O)(2)](2+) to form an S,O-chelate in which the O-coordinated group is either carboxylate or phosphonate, depending on the degree of protonation of the complex. Carboxylate appears to be the stronger ligand, and the stoichiometric reaction between cis-[Pt(NH(3))(2)(H(2)O)(2)](2+) and L(2-) yields the neutral species [Pt(L)(NH(3))(2)], with L bound by sulfanyl and carboxylate groups, both in solution and in the solid state. Upon protonation of [Pt(L)(NH(3))(2)], the stronger basicity of the carboxylate causes the Pt coordination to switch from carboxylate to phosphonate, and the uncoordinated carboxylate group becomes protonated. In methanolic solution, the first-order kinetics of this rearrangement could be observed by (31)P NMR spectroscopy. Both complexes-the carboxylate-bound neutral complex [Pt(L)(NH(3))(2)].H(2)O (triclinic, P1 (no. 2), a=9.529(6), b=9.766(6), c=12.299(7) angstroms, alpha=106.91(2), beta=101.71(2), gamma=102.05(2) degrees, Z=2) and the perchlorate salt of the phosphonate-bound complex [Pt(LH)(NH(3))(2)]ClO(4).H(2)O (monoclinic, P2(1)/c (no. 14), a=12.095(2), b=14.046(2), c=14.448(2) angstroms, beta=95.55(2) degrees, Z=4)-were characterized by X-ray crystallography.

The self-assembly of 1,12-dodecanedinitrile (ddn) with various silver salts (NO(3)(-), PF(6)(-), AsF(6)(-), ClO(4)(-)) afforded new polymeric coordination networks with the general formula [Ag(ddn)(2)]X. All these species contain interpenetrating diamondoid nets showing interesting features: with X=NO(3)(-) the cationic [Ag(ddn)(2)](+) network exhibits the highest interpenetration (tenfold) ever found within diamondoid nets exclusively based on coordinative bonds. When X=PF(6)(-) or AsF(6)(-) an eightfold diamondoid network is obtained that shows an unusual [4+4] mode of interpenetration, instead of the "normal" set of eight nets equally translated along a principal axis of the adamantanoid cages. The polymeric species that forms with X=ClO(4)(-) is a fourfold interpenetrating diamondoid network; the lower degree of interpenetration in this case is related to the conformation assumed by the flexible ddn ligands.