Carboxylates mercury

Another major route to fluorinated organomercury compounds is thermal or photochemical decarboxylation offluonne-conlaining mercury carboxylates [/-Si, 169, 170,171, 172], as shown for example in equation 125 [153, 169] Via similar methodology, C6HjHgCF3 (60-75%) [171], (CF3)2Hg (92%) [/i59T, (02NCFCl)2Hg (58%) [172], and [(CF3)3C]2Hg (80%) [157] were synthesized, and several of these mercurials have been used as fluorocarbene precursors [166],... 

Mercury carboxylates other than Hg(OAc)2 include Hg(OCOCF3)2, which is soluble in nonparticipating solvents such as CH2CI2 and is a more reactive electrophile than Hg(OAc)2 in addition, [Cp3C02] is a poorer nucleophile than [AcO] and does not take part in addition. 

In reactions of mercury(II) salts, the reactivity follows the sequence Hg(OAc)2 > HgCl2 > Hgl2 and electron-attracting groups in the mercury carboxylates accelerate the reaction.41-42 The reactivity follows a steric sequence with respect to the group R being transferred (Me > Et > Pr > Bu1 > Peneo > Pr1), and solvent and salt effects suggest an SE2(C)(open) mechanism. 

Several Hg FT n.m.r. studies of aqueous solutions of Hgl" and Hg " ", organo-mercury carboxylates and chlorides, and dialkylmercury compounds have appeared. Reviews have appeared on the polyatomic cations of zinc, cadmium,... 

In addition to Ag, many other metals (Hg, Pb, Tl, and Mn) can be used in the Hunsdiecker reaction.13-20 The Cristol-Firth modification is a one-pot reaction using excess red HgO and one equivalent of halogen.13 The advantage of the Cristol-Firth modification is that the mercury carboxylate does not need to be isolated and purified, unlike the Hunsdiecker reaction using the silver carboxylate. Therefore, as depicted by transformations 6— 714 and 8— 9,15 the Cristol-Firth modification is operationally more straightforward and more widely used than the classical Hunsdiecker reaction using silver carboxylate 1. 

Tri-n-butylphosphine Carboxylic acid anhydrides from mercury carboxylates... 

N-Mercury adducts 17, 711 Mercury(II) bromide 20, 258, 264 Mercury carboxylates... 

Salicyloylguanidines 19, 459 Salts, exclusive of — 19, 739 —, fused, reactions in — 18, 942 —, inner s. Betaines, Mercury-carboxylic acid inner salts —, organic... 

Aspects of the rhodium-catalysed hydroformylation of olefins have been reviewed. " Copper(ii) acetate catalyses the highly stereoselective solvolysis of -alkenylpentafluorosilicates to -alkenyl ethers under an atmosphere of air. Since the pentafluorosilicates can be obtained via hydrosilylation of acetylenes, the sequence represents a regio- and stereo-selective transformation of acetylenes into carbonyl precursors in moderate yield. The reaction of vinylmercurials and mercury carboxylates catalysed by palladium(ii) acetate provides a stereospecific route to enol carboxylates, which are valuable precursors of specific enolates. ... 

Enol esters (126) can be formed in >70% yields during condensations between thioesters (125) and aldehydes (R CH2CHO) in the presence of caesium fluoride. An alternative approach to esters (126) is to react vinylmercurials, e.g. (127), with mercury carboxylates [(R C02)2Hg] and a catalytic quantity of palladium acetate. A wide range of the organometallic reagents (127) can be obtained from acetylenes by a hydroboration-mercuration sequence. 

The preparation of enol esters in a regio- and stereo-specific manner is important, as they are particularly valuable synthetic intermediates. A room-temperature reaction of vinylmercurials, mercury carboxylates, and a catalytic amount of palladium acetate provides a novel and convenient stereospecific route to a variety of enol carboxylates. ... 

Oxidative addition reactions of mercury carboxylates [Hg(02CR)2] with cis-[Pt(C6H4CH2NMe2-o)a] afford novel stable aryl-platinum-mercury complexes (22) the corresponding rrans-platinum complex forms unstable Pt-H intermediates, which eliminate Hg to leave isomers of [Pt(CeH4CH2NMe2)2-... 

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