Unsymmetrical dirhenium complexes that contain [Re(2)](6+) and [Re(2)](5+) cores complexed by tridentate ligands with P(2)O and P(2)N donor sets.

The quadruply bonded dirhenium(III) complex (n-Bu(4)N)(2)Re(2)Cl(8) reacts with tridentate ligands that contain essentially planar P,O,P donor sets to afford the complexes Re(2)Cl(6)(eta(3)-L(1)) (3) (L(1) = bis[2-(diphenylphosphino)phenyl]ether) and (n-Bu(4)N)[Re(2)Cl(7)(eta(1)-L(2))] (4) (L(2) = 4,6-bis(diphenylphosphino)dibenzofuran). Spectroscopic and electrochemical data support the unsymmetrical structure Cl(4)ReReCl(2)(eta(3)-L(1)) in the case of 3, while 4 contains monodentate P-bound L(2) both complexes contain Re---Re bonds. The synthon cis-Re(2)(mu-O(2)CCH(3))(2)Cl(4)(H(2)O)(2) reacts with ligands L(1), L(2), 2,6-bis(diphenylphosphinomethyl)pyridine (L(3)), bis[2-(diphenylphosphino)ethyl]amine (L(4)), and N,N-bis[2-(diphenylphosphino)ethyl]trimethylacetamide (L(5)) to give the paramagnetic complexes Re(2)(mu-O(2)CCH(3))Cl(4)(eta(3)-L(n)) (5-9) with Re bonds. The lability of the mu-acetato ligands in 5-9 has been demonstrated by the reactions of compounds 5 (n = 1) and 7 (n = 3) with 4-Ph(2)PC(6)H(4)CO(2)H, 2-Ph(2)PC(6)H(4)CO(2)H, and quinoline-4-carboxylic acid to give complexes 10-12 (from 5) and 13-15 (from 7), respectively. These products contain uncoordinated donor atoms that can be used to produce mixed-metal assemblies. Compounds 5 and 7 also react with terephthalic acid (1,4-C(6)H(4)(CO(2)H) to give [Re(2)Cl(4)(eta(3)-L(1))](2)(mu-O(2)CC(6)H(4)CO(2)) (16) and [Re(2)Cl(4)(eta(3)-L(3))](2)(mu-O(2)CC(6)H(4)CO(2)) (17) in which electronic coupling between the paramagnetic sets of dirhenium units is very weak. Single-crystal X-ray structure determinations have been carried out on complexes 5-8, 11, 12, and 14-16.