The behavior of the compound [RuCl(cym)(H2biim)][BAr'4] (cym = eta6-para-isopropylmethylbenzene, Ar' = 3,5-bis(trifluoromethyl)phenyl), synthesized from [[RuCl(cym)]2(mu-Cl)2], H2biim and NaBAr'4, has been studied as a receptor of anions both in solution and in the solid state.

The thermally stable tris(pyridyl) Al(III) complex [MeAl(2-py)3Li·THF] (1·THF), obtained from the reaction of lithiopyridine [2-pyLi] with MeAlCl2 (3:1 molar equiv, respectively), functions as a pyridyl-transfer reagent, as exemplified by the reaction of 1·THF with CuCl (1:1 molar equiv), which gives the Cu(I) organometallic [{Cu(2-py)}3]∞ (2). The solid-state structures of 1, the dimer [MeAl(2-py)3Li]2 ([1]2), and 2 are reported. Complex 2, which cannot be obtained by direct reaction of [2-pyLi] with CuCl, has a polymeric structure in which macrocyclic [Cu(2-py)]3 ring units form infinite offset stacks associated by short Cu···Cu interactions between three- and four-coordinate Cu(I) centers (2.762(3) Å).

The reaction of [ClP(mu-NtBu)]2 (1) with H2O (1 : 2 equivalents) in the presence of excess Et3N gives the new chain compound [(mu-O)[P(mu-NtBu)2P(H)=O]2] (3), consisting of two P2N2 rings linked by a mu-O atom and terminating in P(V)(H)=O groups. A similar chain species is obtained from the reaction of the lithiate of [(tBuNH)P(mu-NtBu)2P(H)=O] (5) with [ClP(mu-NtBu)2P(NHtBu)] (2), the product being [(mu-O)[P(mu-NtBu)2P(NHtBu)]2] (6). Compounds 3 and 6 are the first examples of O-bridged chain phosphazanes and potential precursors to new phosphorus-nitrogen macrocycles. The syntheses and X-ray structures of 3, 5 and 6 are reported.

The in situ reaction of the phosphazane dimer [CIP(mu-N-2-NC5H4)]2 (2) with CuCl in the presence of CsH5N/H2O gives the title complex [(P(mu-N-2-NC5H4))2(mu-O)]2(CuCl x (C5H5N)2)4 (1), containing a tricyclic [(P(mu-N-2-NC5H4))2(mu-O)]2 ligand which is isoelectronic with species of the type [(P(mu-NR))2NR]2.