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

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The main Groups IV and VAcidH 2 PO(OH)Me 2 PO(OH)Me 2 AsO(OH)HPO(OH) 2MePO(OH) 2MeAsO(OH) 2PhAsO(OH) 2PhSbO(OH) 2PO(OH),AsO(OH),sb.o, aq.pK,1.13.16.31.32.33.63.5Very weak2.22.2Very weak6.77.98.38.57.2 12.46.9 11.5one of its modifications. Arylstibonic acids ArSbO(OH) 2 may be preparedsimilarly. The latter are amphoteric as they dissolve in concentrated hydrochloricacid forming the anions ArSbCl;, which may be precipitated as pyridinium salts.Some acid dissociation constants of oxo-acids of P, As and Sb are listed inTable 4.6. While the phosphorus and arsenic compounds are of comparablestrength, the antimony derivatives are very weak acids. Phenylstibonic acid,nominally PhSbO(OH) 2 , is polymeric and insoluble in water, although it dissolvesas a monomer in acetic acid. It probably forms the octahedral anion PhSb(OH); inalkaline solution. In this it resembles not only Sb 2 0 5 which forms Sb(OH); andtelluric acid, which in Te( OH) 6 rather than H 2 TeO 4 , but also related tin complexeswhich form ions Me 2 Sn(OH)~-and MeSn(OH); in strongly alkaline solutions(p.117). There is a general trend for oxoanions to adopt octahedral rather thantetrahedral structures on moving from the First to the Second Long Period.Dimethylarsinic acid crystallizes as hydrogen bonded dimers, similar to thoseformed by carboxylic acids. In solid propylarsonic acid, C 3 H 7 As0(0H) 2 , themolecules are linked together in chains through hydrogen bonds. Arsonic andarsinic acids are readily reduced, in contrast to the phosphorus analogues(Fig. 4.10). By suitable choice ofreagent MeAsO(OH) 2 yields MeAsX 2 , (MeAs)n orMeAsH 2 •MeTable 4.6. Acid dissociation constants of some organooxo-acids+-2.57-' _/O-H------0"' /1 91 .As 1.62 AsMe..Me"'-o------H-o/ ···· ... MeApart from their use as pharmaceuticals (p. 142) organoarsenicals such asalkyl- or arylarsonic acids have found some application as herbicides, fungicidesand bactericides. They are being superseded by the less toxic tin compounds. Allarsenic compounds should be treated as poisonous. The halides cause severeburns on the skin which heal only with difficulty. This property was put to evil use132
RX/NaOH (R = alkyl; Meyer)RN2Cl/NaOH IR=aryl; Bart)RAsO(ONa)zZn/HClRAsO(OH)zS02/HCl/IRAsHLiRAs(NRz)zRAsCLzowRMgXRMgXor RBr + NaRXa1rOHAsMeiR'F:·RMgX-HXR5AsFig. 4.1 O Reactions of organoarsenic compounds. From Principles of OrganometallicChemistry 1968 lst Edn, Chapman and Hali, London. Reproduced by kindpermission of Professor K. Wade who devised this scheme.
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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
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General surveyelements are rapidly
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General surveyCollman, J.P., Hegedu
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100o-100o Si110111Ql-200 . 1L. :1o
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The main group elementsFor R = alky
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The main group elementsweakly exoth
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The main group elementselement and
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The main group elements(a) HYDROSIL
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The main group elementsinsertion:-
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The rnain group elernentsElectrophi
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The first three periodic groupsTabl
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The first three periodic groupstran
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The first three periodic groups(o)(
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The first three periodic groups( b)
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The first three periodic groupsorga
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The first three periodic groupsMe M
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The first three periodic groupsH HE
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The first three periodic groupsThis
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The first three periodic groupsHere
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The first three periodic groupselec
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The first three periodic groupsEt~5
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The first three periodic groupscond
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The first three periodic groupsThe
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1 2·65 1 9-...:..... _;.;;.-c 1·4
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The first three periodic groupsCycl
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The first three periodic groups3. 7
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The first three periodic groupsYe\
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The first three periodic groupsor o
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Table 3.6 Some hydroborating agents
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RCf:0~HH~RCHO2 2Hi~OH-"' 18-C-R/ 1o
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The first three periodic groups(c)
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The first three periodic groupsTHF.
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The first three periodic groupspuls
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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
Page 126 and 127: The main Groups IV and VTable 4.1.
Page 128 and 129: The main Groups IV and Vanes) are s
Page 130 and 131: The main Groups IV and Vconcentrati
Page 132 and 133: The main Groups IV and VTable 4.2.
Page 134 and 135: The main Groups IV and V4.6.3 Caten
Page 136 and 137: The main Groups IV and VTreatment o
Page 138 and 139: The main Groups IV and V4.8 pTC-JJT
Page 140 and 141: The main Groups IV and VA convenien
Page 142 and 143: The main Groups IV and Vfu- +( + )[
Page 144 and 145: The main Groups IV and Vand Me 2 PF
Page 148 and 149: The main Groups IV and Vin World Wa
Page 150 and 151: The main Groups IV and VHX(SblPh M
Page 152 and 153: The main Groups IV and VOn replacem
Page 154 and 155: The main Groups IV and Varsenic yli
Page 156 and 157: The main Groups IV and VPh 2 BiBiPh
Page 158 and 159: The main Groups IV and Vphosphorus
Page 160 and 161: The main Groups IV and VDimethyltin
Page 162 and 163: 5Some transition metalchemistry rel
Page 164 and 165: M L--4----f/~1 11 1\ 11 11 1\ 11 11
Page 166 and 167: Transition metal chemistryeven nega
Page 168 and 169: co co co cooc~o o co c~co cooc~c~ o
Page 170 and 171: Transition metal chemistryeach othe
Page 172 and 173: Transition metal chemistryconsidere
Page 174 and 175: Transition metal chemistryTable 5.3
Page 176 and 177: Transition metal chemistryTable 5.5
Page 178 and 179: Table 5.7. Thermochemical data and
Page 180 and 181: Transition metal chemistryNickel is
Page 182 and 183: Transition metal chemistry(o)(OC ln
Page 184 and 185: Transition metal chemistryCarbonyl
Page 186 and 187: Transition metal chemistry2Cr(COJ6
Page 188 and 189: Transition metal chemistry18-electr
Page 190 and 191: Table 5.8. General reactions of tra
Page 192 and 193: Transition metal chemistry5. 3.1 Ad
Page 194 and 195: 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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