Synthesis, molecular structure and reactivity of a calix[4]arene monomethyl ether supported nitridomolybdenum complex

The calix[4]arene monomethyl ether supported nitridomolybdenum complex [MoN(MeCalix)] (1) was obtained in high yield from the reaction of [MoN(OtBu)(3)] and calix[4]arene methyl ether (H(3)MeCalix). Contrary to the calix[4]arene dimethyl ether supported dioxomolybdenum complex [MoO2(paco-Me(2)Calix)] published earlier, the calix[4]arene ligand in 1 adopts a cone conformation. Complex 1 reacts smoothly with GaCl3 and GaEt3 to yield the compounds [Mo(NGaCl3)(MeCalix)] (2) and [Mo(NGaEt3)(MeCalix)] (3), respectively. Complex 2 is the first structurally characterized example of a nitrido-bridged dinuclear compound of a group 6 metal and a group 13 halide (EX3). The [Mo N-GaCl3] unit, in which both metal atoms are unsymmetrically bridged with a short Mo N and a long Ga-N contact, shows significant bending at the nitrido bridge. This deviation from a linear alignment is attributed to packing forces. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.