_P.-Powell-auth.-Principles-of-Organometallic-Chemistry-Springer-Netherlands-1988

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The first three periodic groups3. 7. 3 Mercuration of aromatic compounds: comparison with thallationK '' xgXArH + HgX2 :;:::::=::: ArH.HgX 2 k_ 1~ +Xn-eom plexcr-complex-*2,8+ -ArHgX + BH +XAromatic compounds undergo electrophilic mercuration. The old methodinvolved heating the arene with mercury(II) acetate under reflux in acetic acid orin ethanol. Recently it has been found that mercury(II) trifluoroacetate intrifluoroacetic acid reacts at room temperature. The reactions are reversible; theisomer ratios depend on time, tending towards the statistica!. The mechanismshown above has been proposed. The equilibrium constant K for n-complexformation has been estimated from changes in the UV spectra of arenes whichoccur on addition of Hg(OCOCF 3 ) 2 • For benzene in CF 3 C0 2 H at 25°C, K =8.2mol- 1 dm 3 •Multiple substitution of reactive aromatic compounds may occur. Thiophenegives a 2, 5-disubstituted and furau a 2, 3, 4, 5-tetrasubstituted derivative withmercury(II) acetate in boiling ethanol. The preferential mercuration of thiophenehas been used for its removal from commercial benzene. Mercuration of ferrocene(p. 284) also occurs readily.Thallation of aroma tic compounds is similar. It is most efficiently carried out byusing thallium(III) trifluoroacetate in trifluoroacetic acid. Reaction is oftencomplete within a few minutes at room temperature; up to two days may berequired for deactivated arenes like chlorobenzene. Thallation, like mercuration,is reversible. The reagent has a large steric requirement which normally hindersortho substitution. With isopropylbenzene, for example the para isomer is formedpreferentially at first but the meta isomer gradually builds up with increasingreaction time. This is a useful method of making meta substituted alkylbenzenes.Where a substituent is able to coordinate to the incoming thallium reagent,however, ortho substitution can result in spite of steric effects (Fig. 3.15 ).The thallium group can be replaced by a wide range of substituents under mildconditions (Fig. 3.16). There is no need to isolate the arylthallium intermediate.Potassium iodide, for example, reacts with ArTl(OCOCF 3 ) 2 to give Ari and TII(insoluble), presumably via unstable ArTli 2 •3. 7.4 Mercuration and thallation of alkenes and alkynes(a) MERCURATION. These reactions are described by the general schemeRCH=CH 2 + HgX 2 + HY ~ RCYHCH 2 HgX + HX(Y = e.g. OH. OR'. OCOR', NR'R"; X= OCOCH, or OCOCF,)Mercury(II) a cetate or trifluoroacetate is most often used. HY is often the solvent;where it is water (Y = OH), the reaction is termed oxymercuration or62
9.,TL(OCOCF3)2thermodynomicproductkinetic productFig. 3.15 Thallation of aromatic compounds.ArNOArPhArN0 2PdCL2NOCLAr-Ar .---NaOcocH3B2H6/aqKFArithen BF 3(95%)ArBrArCLLiBD4 KCN, h\lArOH Cu(CNl21Fig. 3.16 Some reactions of ArTIX 2 •ArD ArCN
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Principles ofOrganometallicChemistr
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© 1988 P. PowellOriginally publish
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Contentsvi3.5 Beryllium 543.6 Calci
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Contents12.4 Chemistry based on syn
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PrefaceIn the 20 years since 'Princ
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Periodic table ofthe elementsThe pe
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Periodic table of elementsGroup Gro
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General surveysyntheses. They are a
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General surveypacked hexagonal, nic
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Table 1.1. Mean metal-carbon bond d
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General survey(c) COMPLEXES OF UNSA
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General survey4008.0o1E...,300.=; 2
Page 26 and 27: General surveyelements are rapidly
Page 28 and 29: General surveyCollman, J.P., Hegedu
Page 30 and 31: 100o-100o Si110111Ql-200 . 1L. :1o
Page 32 and 33: The main group elementsFor R = alky
Page 34 and 35: The main group elementsweakly exoth
Page 36 and 37: The main group elementselement and
Page 38 and 39: The main group elements(a) HYDROSIL
Page 40 and 41: The main group elementsinsertion:-
Page 42 and 43: The rnain group elernentsElectrophi
Page 44 and 45: The first three periodic groupsTabl
Page 46 and 47: The first three periodic groupstran
Page 48 and 49: The first three periodic groups(o)(
Page 50 and 51: The first three periodic groups( b)
Page 54 and 55: The first three periodic groupsorga
Page 56 and 57: The first three periodic groupsMe M
Page 58 and 59: The first three periodic groupsH HE
Page 60 and 61: The first three periodic groupsThis
Page 62 and 63: The first three periodic groupsHere
Page 64 and 65: The first three periodic groupselec
Page 66 and 67: The first three periodic groupsEt~5
Page 68 and 69: The first three periodic groupscond
Page 70 and 71: The first three periodic groupsThe
Page 72 and 73: 1 2·65 1 9-...:..... _;.;;.-c 1·4
Page 74 and 75: The first three periodic groupsCycl
Page 78 and 79: The first three periodic groupsYe\
Page 80 and 81: The first three periodic groupsor o
Page 82 and 83: Table 3.6 Some hydroborating agents
Page 84 and 85: RCf:0~HH~RCHO2 2Hi~OH-"' 18-C-R/ 1o
Page 88 and 89: The first three periodic groups(c)
Page 90 and 91: The first three periodic groupsTHF.
Page 94 and 95: The first three periodic groupspuls
Page 96 and 97: The first three periodic groupsROH/
Page 98 and 99: The first three periodic groupsthe
Page 100 and 101: The first three periodic groupsThe
Page 102 and 103: The first three periodic groupsin p
Page 104 and 105: The first three periodic groupsSilv
Page 106 and 107: The first three periodic groupso-RR
Page 108 and 109: The first three periodic groups(a)(
Page 110 and 111: The first three periodic groups5. W
Page 112 and 113: 4Organometallic compoundsof element
Page 114 and 115: The main Groups IV and Vachieved e.
Page 116 and 117: The main Groups IV and Ve.g. alipha
Page 118 and 119: The main Groups IV and VDimethyltin
Page 120 and 121: The main Groups IV and V4.3.3 React
Page 122 and 123: The main Groups IV and Villustrates
Page 124 and 125: The main Groups IV and Vof methylco
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The main Groups IV and VTable 4.1.
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The main Groups IV and Vanes) are s
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The main Groups IV and Vconcentrati
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The main Groups IV and VTable 4.2.
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The main Groups IV and V4.6.3 Caten
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The main Groups IV and VTreatment o
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The main Groups IV and V4.8 pTC-JJT
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The main Groups IV and VA convenien
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The main Groups IV and Vfu- +( + )[
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The main Groups IV and Vand Me 2 PF
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The main Groups IV and VAcidH 2 PO(
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The main Groups IV and Vin World Wa
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The main Groups IV and VHX(SblPh M
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The main Groups IV and VOn replacem
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The main Groups IV and Varsenic yli
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The main Groups IV and VPh 2 BiBiPh
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The main Groups IV and Vphosphorus
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The main Groups IV and VDimethyltin
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5Some transition metalchemistry rel
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M L--4----f/~1 11 1\ 11 11 1\ 11 11
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Transition metal chemistryeven nega
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co co co cooc~o o co c~co cooc~c~ o
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Transition metal chemistryeach othe
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Transition metal chemistryconsidere
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Transition metal chemistryTable 5.3
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Transition metal chemistryTable 5.5
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Table 5.7. Thermochemical data and
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Transition metal chemistryNickel is
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Transition metal chemistry(o)(OC ln
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Transition metal chemistryCarbonyl
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Transition metal chemistry2Cr(COJ6
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Transition metal chemistry18-electr
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Table 5.8. General reactions of tra
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Transition metal chemistry5. 3.1 Ad
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Transition metal chemistrynot detec
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Transition metal chemistryPd(PPhBu~
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Transition metal chemistryH2 -LL3Rh
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Transition metal chemistryPhosphine
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Transition metal chemistry(d) Comme
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Transition metal chemistryD: 1 Hn.m
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Organometallic compounds of the tra
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No3-electron1] 3 -allyl4-electron17
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Organotransition metal chemistrymel
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Organotransition metal chemistryii)
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Table 7.2. Mechanisms of decomposit
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Organotransition metal chemistry4Ti
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Organotransition metal chemistryM e
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Organotransition metal chemistryIn
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Organotransition metal chemistryThe
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Organotransition metal chemistry~ (
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Organotransition metal chemistryo o
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Organotransition metal chemistry( C
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Organotransition metal chemistryMe
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Organotransition metal chemistry/OM
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Organotransition metal chemistry7.3
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Organotransition metal chemistryexc
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Organotransition metal chemistrysev
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Organotransition metal chemistry)--
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Organotransition metal chemistryR R
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Organotransition metal chemistry-co
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Organotransition metal chemistry4.
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Organotransition metal chemistry(b)
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r~...I.J::...--Î-..L-.._.,:;.I""'
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Allyl and diene complexessignals ar
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Allyl and diene complexesdoublets.
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Allyl and diene complexes111.5°. A
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Allyl and diene complexesThe pallad
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Allyl and diene complexesFe(C0} 5-F
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Allyl and diene complexes~4,neutrat
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Allyl and diene complexesThis indic
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Allyl and diene complexesonly with
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Allyl and diene complexesderivative
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Allyl and diene complexesvolatile,l
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Allyl and diene complexesChemical R
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9Five electron ligands9.1 lntroduct
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Five electron ligandsTable 9.1 The
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Five electron ligandsthe ferriceniu
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Five electron ligandsFerrocene unde
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Five electron ligands---v~···Fe,
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Five electron ligandsDihalogenometh
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Five electron ligands(c) TITANOCENE
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Five electron ligandsa pair of non-
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Five electron ligands9. 3.1 Mononuc
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Five electron ligandsslowly oxidize
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~ o coo,... ...,C,, /....-:;.' //Fe
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Five electron ligandsn-system of ea
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Five electron ligandsFig. 9.15 Mole
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Five electron ligandsNucleophilic r
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Five electron ligands(a) Sketch the
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lCH2=CHC2H5Five electron ligands(i)
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Five electron ligands( 6 A 1 g) and
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Complexes of arenesFor chromium thi
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Complexes of arenesW(C 6 H 6 ) 2
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Complexes of arenesgas phase (5.01
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Complexes of arenes(Q)-RCr cr(C0)
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Complexes of arenes- BH 3~jCr(C0) 3
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Complexes of arenesif"••d•R"x
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wNfoi::>.~7trienyl Cr(C0) 3~·trien
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Complexes of arenesmethyl iodide. T
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Complexes of arenesin the whole mol
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Complexes of arenesproposed above,
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Complexes of arenesProblems1. Ferro
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Complexes of arenes(<) ~PlMe~MeMe~M
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Table 11.1. Electron counting in cl
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Cluster compounds455TrigonalOctahed
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Cluster compoundsFig. 11.4 Closo, a
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Cluster compoundsmixture of the mor
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Cluster compoundsIt is extremely st
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Cluster compounds2- 2-~ m1 11O GQ8-
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Cluster compounds(IJ 5 -C,B,H 6 )Mn
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wUlo2-Fe(C0) 5redu cine;~C 7 H~BF4-
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Cluster compoundsdensations' do not
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Cluster compoundsA 3 A 78 78 12A 3c
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Cluster compoundsstructures of the
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Mechanisms of industrial processesT
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Table 12.2.Process Feedstock Cataly
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Mechanisms of industrial processesF
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Mechanisms of industrial processes1
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chaingrowth(alkeneinsertion)CH 3 CH
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r!~~NiJy ~ ' ,. -;,,.,~,;, ..'Ni'+2
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ţ/Ph)o-cPd =:) )cH0-C'-....Ph 2~-8
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Mechanisms of industrial processesH
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H2 C=CH2H2C=CH2[Ti]-R + C2H4coordin
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o[~] o ~ [f!- ~7:Jlinear[w]=CH~poly
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Me3 CCH2Li3HCI/WCL 6 W(=CBut)(CH2 B
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Mechanisms of industrial processesW
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Mechanisms of industrial processesT
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••~'"'"'" 7 ~;~13 :H~ r--------
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Mechanisms of industrial processesc
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Mechanisms of industrial processesO
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Mechanisms of industrial processesc
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Mechanisms of industrial processesH
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a)oIIIc1c1o1H /H'-cH2 ,l!--1 --H'.
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Mechanisms of industrial processesB
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Mechanisms of industrial processes5
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Lanthanides and actinidesA few exam
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Lanthanides and actinidesCp~LuCH 3
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IndexOrganometallic compounds are i
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IndexCarbon monoxide contd.bonding
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IndexEthylene glycol. see Ethane-1.
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IndexMetallocenes contd.reactions,
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IndexSilicon contd.-silicon bonded
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_P.-Powell-auth.-Principles-of-Organometallic-Chemistry-Springer-Netherlands-1988

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