Mercury transition metal complexes

Atwood DA, Zaman MK (2006) Mercury Removal from Water 120 163-182 Autschbach J (2004) The Calculation of NMR Parameters in Transition Metal Complexes 112 1-48... 

Metallotropic rearrangement, in mercury tri-azenide complexes, 30 41 Metals, see also Heterobimetallics specific element Transition metal complex alkoxides, 15 159-297 of actinides, 15 290-293 of alkali metals, 15 260-263 of alkaline earths, 15 264-266 of aluminium, 15 266-272 of beryllium, 15 264-266 double type, 15 293-294 of gallium, 15 266-272 of lanthanides, 15 290-293 of magnesium, 15 264-266 properties of, 15 260 of transition metals, 15 272-290 trialkylsilyloxides, 15 295-297 of zinc, 15 264-266... 

Transition metal complexes with mercury directly bound to one or two transition metal centers are well known.1 They have found use as relatively air-stable sources of carbonyl metallate anions in polar solvents and as intermediates in the syntheses of bimetallic transition metal complexes. They are probably the key intermediates in the many transition metal promoted... 

Aminoboranes have been used as ligands in complexes with transition metals (66) in one instance giving a rare example of two-coordinate, non-/0 transition-metal complexes. The molecular structure of the iron complex Fe[N(Mes)B(Mes)2]2 where Mes = 2,4,6-(CH3)3C5H2 is shown in Figure 1. The less sterically demanding lithium borylamide, LiN(CH3)B(CH3)2, used to prepare mercury and tin complexes, has also been prepared (67). 

Table 1 Some Mercury-containing Transition Metal Complexes...

Phosphorus magnetic shielding tensors, general phosphido ligands in transition metal complexes, 1, 472 Phosphorus(III) mercury compounds, preparation, 2, 425-426 Phosphorus—metal complexes, characteristics, 2, 34 Phosphorus—nitrogen-containing rings, chromium carbonyl link, 5, 225... 

Other metals for which complexes of ligand 79 have been isolated are iron(II)48, 5s, 56,58,59) ir0n(III) 47,52, s4, s6> 59), zinc(II) 57 59), cadmium(II) 59,60,78), mercury(II) 58,78), magnesium(II) S9 60), manganese(II)58>, nickel(II)79), and lead(II)80). The reduction of bis-amws 79 has been reported to afford ligand 81. In addition, the transition metal complexes of iron(III), cobalt(III), nickel(II), and copper(II) with ligand 81 have been prepared and characterized 53). 

This method was successfully applied using acetates [64,65], acetylacetonates [66,67], alkoxides [16,68,69] and [Pd2(dba)j] [70]. In fact, the first NHC transition metal complex reported by WanzUck and Schonherr in 1968 [3] used mercury(II) acetate and 1,3-diphenylimidazolium perchlorate as the starting materials. 

Bildstein et al. have previously shown that Fc functionalised NHC (annulated and nonan-nulated) can be successfully employed to synthesise a broad range of transition metal complexes [166]. These include palladium, tungsten and mercury. Interestingly, two different species of mercury NHC complexes could be synthesised and structurally characterised (see Figure 4.49), with the dinuclear complex being the precursor for the mononuclear one. 

Overall, many transition metal complexes have been investigated. Among those not mentioned above which may carry out catalytic allylic oxidation to give enones under certain drcumstances are Co(PPh3)Cl/02, Mn(TPP)Cl/02, [Fe(PPh3)]20AJV, Ni(phthalocyanine)/02 and an unusual mercury(II) acetate example in which the enone is formed rather than the expected acetate. 

Inner-Transition Metal to Transition and Inner-Transition Metal Bond 105 9.2.12. Inner Transition Metal Complexes With Chains of Metal Atoms 9.2.12.3. Compounds Containing Mercury Chains... 

The catalytic activity of Hg in elimination and substitution reactions of transition-metal complexes continues to be the subject of study. Kinetic studies on the Hg" catalysed aquation of both cis-[Co(en)2(CN)Cl], cis-[(chloro)(aniline)CO(en)2], and [PdLX] (L = tetramethyldiethylenetriamine X = Cl, Br, or I) are consistent with intermediate adduct formation at the halide substituent. Mercury(ii) reacts reversibly with the [Co(NH3)5SCN] ion to yield [Co(NH3)5(SCN)Hg] which irreversibly undergoes either aquation to yield [Co(NH3)sH20] or isomerization to yield [Co(NH3)5(NCS)Hg] at approximately equal rates. The kinetics of the reaction... 

Organomercurials can also be used for the synthesis of alkyl complexes. Organomercurials have stable alkyl-mercury bonds, and the alkyl groups can be transferred to transition metal complexes (alkylation of the transition metal complexes). Thus diphenylmercury reacts with one equivalent of dichloroplat-inum complex to produce phenylmercuric chloride and monosubstituted platinum complex in good yield 73). 

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