Alkylimido and oxo aryls of rhenium. X-ray structures of (BuittN)2ReCl2(o-MeC6H4) and MO2(2,6-Me2C6H3)2, M = Re and Os

High oxidation state organomolybdenum and organotungsten chemistry in protic environments

“…Early anhydrous oxidation routes involve thermal or photochemical reactions with O 2 , whereby [Cp 2 Mo 2 (CO) 6 [75][76][77], the hydrolytic synthesis of the oxido derivatives has been further optimized [78]. The procedure is in fact a convenient entry to the Mo VI derivative [Cp 2 Mo 2 O 5 ], which is obtained by further oxidation of the CpMo V oxido products.…”

“…This protocol is also effective when using higher oxidation state starting materials, e.g. compound [ 6 ] is shown in Scheme 5. A short-cut consisting of a three-step, one-pot procedure has recently been reported [96].…”

“…A short-cut consisting of a three-step, one-pot procedure has recently been reported [96]. This involves the direct oxidation of Na[Cp * M(CO) 3 ], formed in a first step from [M(CO) 6 ] and NaCp * , with tBuOOH in water [96]. It saves two steps with respect to the procedure of Ref.…”

“…They comprise homoleptic compounds such as [W(CH 3 ) 6 ] [1] and [Re(CH 3 ) 8 ] 2− [2], and complexes that also contain other electronegative ligands, such as oxido (e.g. [ [2] thermally decompose at room temperature or below and react rapidly with water and other compounds containing acidic hydrogens to give methane.…”

“…We only wish to mention three trinuclear alkylidyne-capped Mo compounds, [Mo 3 (CCH 3 ) 2 (O 2 CCH 3 ) 6 (H 2 O) 3 ] n+ (n = 1, 2) [28,29] and [Mo 3 O(CCH 3 )(O 2 CCH 3 ) 6 (H 2 O) 3 ] + [30], reported several years ago by Cotton and Bino, which are fully compatible with an aqueous environment. The [Mo 3 (CCH 3 ) 2 (O 2 CCH 3 ) 6 (H 2 O) 3 ] 2+ complex spontaneously couples the two alkylidyne moieties in aqueous solution at room temperature to yield 2-butyne [31]. A 2 (CH 3 C CCH 3 )], has been isolated by carrying out the reaction in the presence of HBr, and crystallographically characterized [31].…”