Thallium hexafluorophosphate

The (IsQ-coordinated species [Mo(CO)3(py)3] prepared from [Mo(CO)6] and pyridine is useful for the synthesis of various jr-allyl molybdenum compounds (68JOM(13)Pl, 970M5365). The 3-allyl complexes [( 3-allyl)Mo(CO)2Br(py)2] form [( 3-allyl)Mo(CO)2(S,S)(py)] with the anionic S,S-donors, dithiocarbamates and xanthates of sodium and potassium, M (S,S) (81JOM(218)185). [( 3-C3H5)Mo(CO)2(py)2Br] (68JO M(14)375) with thallium hexafluorophosphate in acetonitrile gives... 

Catalyst 1, [(z7 -crotyl)(cycloocta-l,5-diene)nickel]hexafluorophosphate ( naked nickel ), was prepared following a procedure developed for the methallyl isomer by Tkatchenko and coworkers [35, 37]. Thus bis(cyclo-l,5-octadiene)nickel was reacted with crotyl bromide to yield the bromide-bridged (// -crotyl)nickel dimer. Abstraction of the bromide by thallium hexafluorophosphate in the presence of cyclo-1,5-octadiene yielded 1. The structure of 1 in solution is consistent with its solid state X-ray crystal structure [38]. 

Hexamethylphosphoramide (HMPA 0.1 ml, 0.575 mmol) was added to a stirred solution of bromodiphenylbismuthine (0.127 g, 0.287 mmol) in THE (5 ml) at room temperature to give a eolorless solution. A solution of thallium hexafluorophosphate (0.100 g, 0.287 mmol) in the same solvent (6 ml) was added and led to the immediate formation of a pale yellow precipitate. The mixture was stirred for 30 min and then filtered through Celite to give a slightly eloudy filtrate which was reduced to about 5 ml in volume under vacuum. Hexane (20 ml) was added as an overlayer, and solvent diffusion, over a period of several days at — 22°C, afforded the complex as colorless crystals in 76% yield [96JCS(D)443]. 

The direct conversion of carbyne complexes TpW( = CR)(CO)2 (R = Ph, C6H4Me-4) to cationic c/ -dicarbonyl -phosphinocarbene (metallaphosphacyclo-propene) complexes can be achieved by the addition of chlorodiorganophosphines in the presence of sodium tetraphenylborate or thallium hexafluorophosphate (Scheme 51)/ In the absence of these sodium salts, nucleophile (Cl )-induced carbonyl-carbene coupling affords neutral -phosphinoketene complexes. 

Caution. Thallium hexafluorophosphate is toxic and should be handled in a hood. 

Most recently, Cramer and Jenkins have developed a novel tetracarbene iron(ll) complex 8, which was readily prepared by the reaction of the macrocyclic tetraimidazolium 7 with iron(ll) iodide using lithium diisopropylamide followed by the addition of thallium hexafluorophosphate (Scheme 2.12) [18]. Employing this catalyst system, aziridination reactions of various types of substituted aliphatic alkenes including trisubstituted and tetrasubstituted ones with both electron-donating and electron-withdrawing aryl azides were achieved. One advantage of this methodology is... 

KETONES Lithium diisopropylamide. Nickel carbonyl. Sodium tetiacarbonyl-ferrale(-II). Thallium(IIl) nilrale. 2,4,4,6-Tetramethyl-5,6-dihydro-l,3-(4/0-oxazine. Triphenylmcthyl hexafluorophosphate. y-KETONlTRILES Sodium cyanide. d-LACTONES Silver nitrate. 7-LACTONES a-Chloro-N-cyclohexylpro-panaldoximc. 

CIFgN4PZnC24H2g, Zinc(II), chloro(2,9-di-methyl-3,10-diphenyl-l, 4,8,11-tetraaza-cyclotetradeca-1,3,8,10-tetraene)-, hexafluorophosphate(l -), 22 111 CIFgTlCi2H2, Thallium(III), chlorobis-(2,3,4,6-tetrafluorophenyI-), 21 73 CIF9OC4, Hypochlorous acid, perfluoro-tert-butyl ester, 24 61... 

In a similar manner, the reaction of 1 -rcr/-butyl-2,3-diphenylcyclopropenylium hexafluorophosphate (19) with hexacarbonyltungsten(O), followed by treatment with thallium cyclopentadienide, gave the tungsten complex 20. ... 

Secondly, Oberbeckmann-Winter et al. [90, 91] observed the formation of a cationic bimetallic species instead of the expected chloride abstraction when the benzylplatinum(II) complex depicted in Scheme 24 (bottom) was treated with thallium(I) hexafluorophosphate in dichloromethane. The starting platinum complex acted as a chelating metalloligand, coordinating to thallium via both the platinum atom and the aromatic ring. Again, exposure of the bimetallic intermediate to the more polar solvent acetonitrile released TlCl. 

---