Synthesis of (pentamethylcyclopentadienyl)nitrosylmolybdenum complexes containing halide, methyl, or cyclopentadienyl ligands. Crystal structures of [MoMe(η-C₅H₅)(η-C₅Me₅)(NO)] and [{Mo(η-C₅Me₅)O(µ-O)}₂]

Cyclopentadienylmolybdenum(VI) and Molybdenum(V) Oxo Chemistry: New Synthetic and Structural Features

“…It seemed that not only the time of exposure to air but also the relative amount of water and acetone was important in determining the ratio between the Mo V and Mo VI products (see Discussion), smaller amounts of water seeming to favor a greater degree of oxidation. [Cp*MoO 2 ] 2 has been reported previously and shown to adopt two possible structures differing in the relative arrangement of the Cp* and terminal oxo ligands across the central Mo(μ‐O) 2 Mo plane: syn as in I 38 (like the analogous Cp system)39 or anti as in II 40. We have redetermined the structure of the syn form at lower temperature with a better precision.…”

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

“…671 956 The linked Cp complex [Cr 2 (CO) 6 (r|,r|-C 5 H4CH2C 5 H4)] reacts in an analogous manner to those above. 957 Access to the analogous Cp* chemistry can be gained through reaction o f [Cr(CO) 3 Cp*]~ with trithiazyl chloride (N 3 S 3 C1 3 ).…”

“…The synthesis of the mixed complex [Mo(NO)(X)CpCp*] has also been achieved. 671 The first terminal phosphinidene complexes, [M(=PMes*)Cp 2 ] (41), have been prepared from [M(H)(Li)Cp 2 ] 4 and Mes*PCl 2 ; they display extremely low-field 31 P NMR shifts o f 799.5 and 666.1 ppm for molybdenum and tungsten, respectively. 1334 The related [W(=PNHMes*)Cp* 2 ] was prepared by an analogous route.…”

Cyclopentadienylmolybdenum(VI) and Molybdenum(V) Oxo Chemistry: New Synthetic and Structural Features

“…It seemed that not only the time of exposure to air but also the relative amount of water and acetone was important in determining the ratio between the Mo V and Mo VI products (see Discussion), smaller amounts of water seeming to favor a greater degree of oxidation. The metal-metal distance in the syn polymorph [2.587(1) Å ] is significantly shorter than that in the anti polymorph [2.647(3) Å ], [40] undoubtedly because of the butterfly arrangement that allows the metals to approach each other, in contrast to the planar arrangement in the anti isomer. [40] We have redetermined the structure of the syn form at lower temperature with a better precision.…”

“…[40] This parameter is therefore much more sensitive to the geometry of the central Mo 2 O 2 moiety (bent for the syn and planar for the anti) than to the type of cyclopentadienyl ring. [40] This parameter is therefore much more sensitive to the geometry of the central Mo 2 O 2 moiety (bent for the syn and planar for the anti) than to the type of cyclopentadienyl ring.…”