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

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RCf:0~HH~RCHO2 2Hi~OH-"' 18-C-R/ 1oldehydeorketone PyH+Cr0 3 CLsituR 3 COHROHR2CONo reaction H20 arOH OHat 25°C oq HXRCH2C02EtKOBu+AgN03R'co2HRHR-RRHgOAcOAL(0Me)3~ [ R3cso]3 H2o2;H O fR C-BR ~21 1 OH-BrCH2C02Et fHg(0Acl2Fig. 3.18 Cleavage of::::: B-R bonds useful in organic synthesis.RNH 2 .H20 2 1 0H- 1 ClNH 2
BuC=CH + H,B·THF----> BuCH 2 CH(B <) 271Organoboron compoundsThe carbonylation of organoboranes presumably proceeds via a weak complexR 3 B · CO which rearranges in a similar way to an acylborane. This can beconverted as shown into a variety of organic products. In severa! of thesereactions, however, only one or two of the three R groups on boron are used.Similarly alkynyltrialkylborate ions. on protonation and oxidation yieldketones or tertiary alcohols according to the conditions.HCI R~ H20 2//C=CH2R 2 B 1aq.HCIOHRCOCH 3 (ketone)RB-CR2CH31H202/OHOH OHR2CCH 3 ( terliory olcohol)As well as being hydroborating agents, boron hydrides can reduce certainfunctional groups. In Table 3.8 the behaviour of BH 1 and of 9-BBN in THF iscompared with that of some other common hydridic reagents. It is thereforenecessary to 'protect' groups such as -CHO, -COR and -CN ifthey are presentin a molecule which it is intended to hydroborate.The hydroboration of alkynes leads in the first instance to alkenylboranes. Inthe absence of sufficient steric effects, however, these react further. UsingH 3 B · THF, for example, 1-alkynes give predominantly diboron derivatives.1
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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
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 76 and 77: The first three periodic groups3. 7
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 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
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.
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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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