The Combination of Organometallic {Mo(η³-allyl)(CO)₂(phen)} Fragments and Hard Aquo and Hydroxo Ligands:  Controlled Synthesis and Structural Characterization

Abstract

The reaction of [Mo(η 3 -C 3 H 4 -Me-2)Cl(CO) 2 (phen)] with NaBAr′ 4 (Ar′ ) 3,5-bis(trifluoromethyl)phenyl) and H 2 O allowed the isolation of the aquo complex [Mo(η 2), which could be also obtained by reaction of [Mo(η 3 -C 3 H 4 -Me-2)Cl(CO) 2 (phen)] with KOH in a biphasic CH 2 Cl 2 / H 2 O medium. The reaction of 1 and 2 afforded the binuclear hydroxo-bridged compound [{Mo(η 3 -C 3 H 4 -Me-2)(CO) 2 (phen)} 2 (µ-OH)]BAr′ 4 (3b) via nucleophilic substitution of water by the hydroxo ligand.

Reactivity of Molybdenum and Rhenium Hydroxo‐Carbonyl Complexes toward Organic Electrophiles

“…It is proposed that the m-OH group is stabilized because it is located in a hydrophobic environment between the two OEP planes. [26] A similar disposition of the OH bridge between the two eclipsed phenanthroline planes was found in [{Mo(h 3 -methallyl)(CO) 2 (phen)} 2 (m-OH)] + , [14] but in 3-BF 4 , which has staggered bipy ligands, this feature is absent. The presence of an additional ring in the phenanthroline example could lead to a greater p-stacking stabilization, and may account for this difference.…”

“…Elemental analyses were obtained by using a Perkin-Elmer 240-B microanalyzer. The IR spectra were recorded on a Perkin-Elmer FT 1720-X spectrophotometer, while the 1 [14] and [Re-(OTf)(CO) 3 (NÀN)] [44] were synthesized according to literature procedures.…”

“…These ideas, as well as the paucity of previous studies in this area prompted us to explore the reactivity of the hydroxo complexes [Mo(OH)(h 3 -allyl)(CO) 2 (phen)] and [Re(OH)(CO) 3 (NÀN)], the results of which we now wish to report. [13] Results and Discussion [14] The same conditions allowed the preparation of [Re(OH)(CO) 3 (NÀN)] (NÀN = bipy, 2 a; 4,4'-dimethyl-2,2'-bipyridine, Me 2 Àbipy, 2 b) complexes from triflato precursors. [15,16] In contrast, the binuclear hydroxobridged compound [{Re(CO) 3 (bipy)} 2 (m-OH)]OTf (3-OTf) was obtained (Scheme 1) after 12 h when anhydrous CH 2 Cl 2 was used.…”

“…[14] Most hydroxo-bridged complexes possess either several OH bridges or additional bridging groups.…”

A Neutral Organometallic Fluoro Complex Can Be a Good Ligand

“…Thus, crystallization of the crude reaction product from dichloromethane/diethyl ether afforded a high yield of analytically pure 2. 6 ], [12] respectively. A medium intensity band at 446 cm À1 in the IR spectrum of solid 2 was assigned to the MoÀF stretch.…”