SYNTHESES AND CRYSTAL-STRUCTURES OF COMPLEXES [L'O(H2O)V-(MU-O)WO2L]CL(CLO4) AND [L'(ACAC)MO-III(MU-O)MO-VIO2L'][BPH4]2 (L,L' = 1,4,7-TRIAZACYCLONONANE AND ITS 1,4,7-TRIMETHYL DERIVATIVE, ACAC = PENTANE-2,4-DIONATE)

Reaction of an equimolar mixture of [VCl3L'] and [WO3L].3H2O in MeOH-water (4:1) in the presence of air affords upon addition of NaClO4 blue [L'O(H2O)V(IV)(mu-O)W(VI)O2L]Cl(ClO4) 1 (L' = 1,4,7-trimethyl-1,4,7-triazacyclononane; L = 1,4,7-triazacyclononane). Crystals of 1 are monoclinic, space group P2(1)/c, with a = 9.401(8), b = 20.61(1), c = 13.53(1) angstrom, beta = 102.47(7)-degrees, and Z = 4. The complex is an asymmetric, heterodinuclear species consisting of vanadyl VOL'(OH2) and cis-LW(VI)O2 units which are asymmetrically bridged by an oxygen. A suspension of [Mo(III)Br3L'] and excess of sodium penta-2,4-dionate (acac) in water reacts in the presence of air with formation of the asymmetric mixed-valence species [L'(acac)Mo(III)(mu-O)Mo(VI)O2L']2+. The bis(tetraphenylborate) salt 2 crystallizes in the monoclinic space group P2(1)/a with a = 18.589(9), b = 18.30(1), c = 20.432(9) angstrom, beta = 104.73(4)-degrees and Z = 4. The L'Mo(III) (acac) and cis-L'MoO2 units are linked by an asymmetric-mu-oxo bridge with Mo(III)-O(oxo) and Mo(VI)-O(oxo) distances of 2.034(4) and 1.808(4) angstrom, respectively.