Remarkably inert metal alkyl linkages in alkyl dioxo complexes of molybdenum and tungsten

Abstract

Protonic acids such as H202(aq) or HCI in Et20 transform one of the M=O linkages and not the M-C B bonds of CP'M(O)~R complexes [Cp' = Cp (v5-C5H5) or Cp" (v5-C5Me5); M = Mo or W; R = CH2SiMe3 or Me].The respective oxo peroxo and oxo dichloro product complexes Cp'M(0)(v2-02)R and Cp * W(O)(CI),R are isolable in good yields as air-stable crystalline solids that have been fully characterized by conventional methods, including a single-crystal X-ray crystallographic analysis of

(η5-Cyclopentadienyl)oxo(peroxo-O,O')(trimethylsilylmethyl)tungsten and the Related (η5-Pentamethylcyclopentadienyl)oxo(peroxo-O,O')(trimethylsilylmethyl)tungsten-Tetracyanoethylene (2/1)Complex

“…All these dimensions are close to those in related (trimethylsilylmethyl)tungsten complexes (Legzdins, Rettig & Sfinchez, 1985;Legzdins, Phillips, Rettig, S~inchez, Trotter & Yee, 1988). Since the TCNE molecule in (2) is disordered over two orientations, the dimensions are not accurately determined, but they are not far from normal values (Masnovi, Kochi, Hilinski & Rentzepis, 1985;Blackstock & Kochi, 1987) (Table 2).…”

Coordinatively and Electronically Unsaturated Pentamethylcyclopentadienyliridium(III) Complexes with the Dianions of Biuret, of the Diamide of Malonic Acid and of anN-Acetyldipeptide Ester

“…Closely related to these new compounds are Grotjahn's Cp* complexes with the dianions of N-acyl and N-sulfonyl α-amino acids. [ [CpM(NO)L] (M ϭ Mo, W), [11] [CpMo(PR 3 ) 2 Cl], [12] [(arene)Ru(SR) 2 ], [13] [CpCo (1,2-ethylenedithiolato)], [14,15] [Cp*Ru(PR 3 )OR], [16] [Cp*Ru(R 2 NCH 2 CH 2 NR 2 )] ϩ , [17] [M(CO) 3 (O,S-C 6 H 4 )] 2Ϫ and [(OC) 3 MS 2 C 6 R 4 ] 2Ϫ (M ϭ Cr, Mo, W). [18] Noyori's coordinatively unsaturated halfsandwich complex [(arene)RuNHCH(Ph)CH(Ph)-NSO 2 C 6 H 4 Me] is an efficient catalyst for asymmetric hydrogen transfer to ketones.…”

Unusual reaction of a tungsten alkylidyne complex with water. Formation, characterization, and crystal structures of oxo trimers

“…microelectronic industry. Such reactions with water have attracted much attention [4][5][6][7][8][9][10][11][12][13]. Schrock, Lippard and coworkers reported the formation of the dimer W 2…”

“…microelectronic industry. Such reactions with water have attracted much attention [4][5][6][7][8][9][10][11][12][13]. Schrock, Lippard and coworkers reported the formation of the dimer W 2 O 3 (CH 2 CMe 3 ) 6 and (NEt 4 )[WO 3 (CH 2 CMe 3 )] from the reactions of H 2 O with W(CH 2 CMe 3 ) 3 (CCMe 3 ) and W(CCMe 3 )(OCMe 3 ) 3 , respectively (Scheme 1) [4,5].…”

“…CMe 4 was a product in these reactions. Legzdins [7]. Gamble and Boncella reacted an alkylidene complex with HBF 4 -H 2 O to give an oxo alkyl complex [8].…”