Triphenylphosphine tungsten

Tetrachlorobis(triphenylphosphine)tungsten(IV) (4.5 g, 53 mmole) and 1,2-bis-(diphenylphosphino)ethane (2.1 g, 5.3 mmole) are heated in toluene (50 mL, distilled from sodium) at 70° for 3 hours in a 100-mL flask carrying a reflux condenser. The resulting yellow-green solid is filtered using a Schlenk filter, washed with toluene (30 mL) and diethyl ether (30 mL), and dried (10 2 torr, 20°). Yield 2.4 g, 89% it is sufficiently pure for subsequent preparations. Anal. Calcd. for C26H24C14P2W C, 43.1 H, 3.3. Found C, 44.5 H, 3.6. 

Thus, pentacarbonyl(triphenylphosphine)tungsten reacts with methyllithium ... 

C30H19CI3NO4PW, Tricarbonylchloro(5,7-dichloro-8-quinolinato-N,0(1-))(triphenylphosphine)tungsten(II), 46B, 1193 C30H20CI2CU2N6O2 r 1-(2-Pyridylazo)-2-naphtholatochlorocopper(II), 44B, 1009... 

C47H34C13N03P2W DicarbonyIchloro[5,7-dichloro-8-quinolinolato-7VO(l — )]bis(triphenylphosphine)tungsten(ii) W, 590... 

In addition to the successful reductive carbonylation systems utilizing the rhodium or palladium catalysts described above, a nonnoble metal system has been developed (27). When methyl acetate or dimethyl ether was treated with carbon monoxide and hydrogen in the presence of an iodide compound, a trivalent phosphorous or nitrogen promoter, and a nickel-molybdenum or nickel-tungsten catalyst, EDA was formed. The catalytst is generated in the reaction mixture by addition of appropriate metallic complexes, such as 5 1 combination of bis(triphenylphosphine)-nickel dicarbonyl to molybdenum carbonyl. These same catalyst systems have proven effective as a rhodium replacement in methyl acetate carbonylations (28). Though the rates of EDA formation are slower than with the noble metals, the major advantage is the relative inexpense of catalytic materials. Chemistry virtually identical to noble-metal catalysis probably occurs since reaction profiles are very similar by products include acetic anhydride, acetaldehyde, and methane, with ethanol in trace quantities. 

B. DIC ARBONYL(fi5-C Y CLOPENT ADIEN YL) (TETR AFLUORO-BORATO) (TRIPHENYLPHOSPHINE)MOLYBDENUM AND TUNGSTEN, MCp(CO)2(PPh3)(FBF3)(M = Mo, W)4... 

Dicarbonyl(ti5-cyclopentadienyl)hydrido(triphenylphosphine) molybdenum and -tungsten... 

BClFjIrOP jnHjj, Iridium(III), carbonyl-chloromethyl[tetrafluoroborato-(1 - )]bis[triphenylphosphine)-, 26 118 BF4, Borate(l-), tetrafluoro-molybdenum and tungsten complexes, 26 96-105... 

OjBFjPWCvsHa, Tungsten, dicarbonyl(r s-cyclopentadienyl)[tetrafluoro-borato(l - )](triphenylphosphine)-, 26 98... 

Bromopentacarbonylmanganese, 49 tom -Bromotetracarbonyl(methyl-methylidyne)chromium, 50 frmethylidyne)tungsten, 49 Carbonylhydridotris(triphenylphosphine)-rhodium(I), 329 Chromium carbonyl, 51 Decacarbonyldimanganese, 49 Dicarbonylcyclopentadienylcobalt, 96 Dicarbonyl(cyclopentadienyl)[(dimethyl-sulfonium)methyl]iron(II) tetrafluoroborate, 98... 

Diphenyl telluroketone was generated, when pentacarbonyl(diphenylmethylene)tungsten reacted with bis[triphenylphosphine]iminium tellurocyanate3. The telluroketone remained coordinated to the tungsten. 

Pentacarbonyl(diphenyl telluroketone)tungsten(II)3 Under dry nitrogen solutions of 980 mg (2 mmol) of pentacarbonyl(diphenylmethylene)tungsten in 20 ml of dichloromethane and of 1.38 g (2 mmol) of bis[triphenylphosphine]iminium tellurocyanate in 10 ml of dichloromethane, both at — 90°, are combined and stirred for 10 min at that temperature- The mixture is then chromatographed on silica gel at — 50° with pentane/dichloromethane (10 1 v/v) as the mobile phase. The blue fractions are collected, the solvent is distilled under high vacuum, and the residue is recrystallized from pentane, yield 220 mg (18%) m.p. 35° (dec.). 

---