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

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Table 11.1. Electron counting in clustersPolyhedral electron countDescriptionVerticesFacesEdgesRestrictionon nMain TransitionGroup Metal MixedRingsPolyhedraDeltahedraClosoNidoArachnoHyphonn2(n + 4)/2n3n/2n;;.3n;;.4n evenn 2n- 4 3(n- 2) n;;;. 5Mn cluster occupies n corners of an (n + 1) cornered deltahedronMn cluster occupies n corners of an (n + 2) cornered deltahedronMn cluster occupies n corners of an (n + 3) cornered deltahedron6m 16t 6m+ 16tSm lSt Sm+ lSt4m+2 14t+2 4m+ 14t+ 24m+4 14t+4 4m+ 14t+44m+6 14t+6 4m+l4t+64m+8 14t+ 8 4m+l4t+8m = number of Main Group atoms in cluster; t = number of transition metal atoms in cluster. m + t = n = number of vertices.
Structure and bondingTetrahedron Prismane Cubane Cuneane DodecahedraneFig. 11.1 'Electron precise' clusters.triangular faces are included in these polyhedra. Euler's theorem for polyhedrastates that the number of vertices + the number of faces = the number of edges + 2(Table 11.1 ). As a consequence ( CH)" clusters can arise only with evenvalues of n.11.2. 2 Deltahedral clustersThe largest group of polyhedral clusters formed by Main Group elements arebased on figures having triangular faces only (deltahedra) (Fig. 11.2). Most ofthem are derived formally from the borane anions B"H~-, but they also includesome metal clusters such as Sn~- and Ge~-. The existence of the eicosahedralanion B 12 H~; was predicted by Longuet-Higgins and Roberts from molecularorbita! calculations a few years before its preparation. The B-H fragmentpossesses four valence electrons in ali ( three from B and o ne from H) of which twoare used to form the B-H bond. It therefore has three orbitals but only twoelectrons left for skeletal bonding. Adoption of deltahedral structures maximizesthe number of nearest neighbours and permits the most efficient electrondelocalization within the cluster. As the grouping CHis isoelectronic with BH-,the treatment covers the carboranes B"_ 2 C 1 H" as well as the borane anionsB"H~-. BH 2 can also be formally replaced by CH, giving rise to further carboranes.The frontier orbitals of a B-H unit consist of a spz type hybrid directed towardsthe centre of the polyhedron and two orbitals (px, Pvl which lie tangential to itssurface. The n radial orbi tais of the former set combine together to give m.o.s of'H--B())-,Xywhich the lowest lying in-phase combination is strongly bonding in character.The approximate spherical symmetry ofthe cluster and ofthe interacting orbitalsleads to the result that (as in an atom) the other radial m.o.s are sphericalharmonics ofthis lowest orbita! (Sa. one orbita!) and have symmetries resembling337
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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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The first three periodic groupsROH/
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The first three periodic groupsthe
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The first three periodic groupsThe
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The first three periodic groupsin p
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The first three periodic groupsSilv
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The first three periodic groupso-RR
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The first three periodic groups(a)(
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The first three periodic groups5. W
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4Organometallic compoundsof element
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The main Groups IV and Vachieved e.
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The main Groups IV and Ve.g. alipha
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The main Groups IV and VDimethyltin
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The main Groups IV and V4.3.3 React
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The main Groups IV and Villustrates
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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
Page 300 and 301: Five electron ligands---v~···Fe,
Page 302 and 303: Five electron ligandsDihalogenometh
Page 304 and 305: Five electron ligands(c) TITANOCENE
Page 306 and 307: Five electron ligandsa pair of non-
Page 308 and 309: Five electron ligands9. 3.1 Mononuc
Page 310 and 311: Five electron ligandsslowly oxidize
Page 312 and 313: ~ o coo,... ...,C,, /....-:;.' //Fe
Page 314 and 315: Five electron ligandsn-system of ea
Page 316 and 317: Five electron ligandsFig. 9.15 Mole
Page 318 and 319: Five electron ligandsNucleophilic r
Page 320 and 321: Five electron ligands(a) Sketch the
Page 322 and 323: lCH2=CHC2H5Five electron ligands(i)
Page 324 and 325: Five electron ligands( 6 A 1 g) and
Page 326 and 327: Complexes of arenesFor chromium thi
Page 328 and 329: Complexes of arenesW(C 6 H 6 ) 2
Page 330 and 331: Complexes of arenesgas phase (5.01
Page 332 and 333: Complexes of arenes(Q)-RCr cr(C0)
Page 334 and 335: Complexes of arenes- BH 3~jCr(C0) 3
Page 336 and 337: Complexes of arenesif"••d•R"x
Page 338 and 339: wNfoi::>.~7trienyl Cr(C0) 3~·trien
Page 340 and 341: Complexes of arenesmethyl iodide. T
Page 342 and 343: Complexes of arenesin the whole mol
Page 344 and 345: Complexes of arenesproposed above,
Page 346 and 347: Complexes of arenesProblems1. Ferro
Page 348 and 349: Complexes of arenes(<) ~PlMe~MeMe~M
Page 352 and 353: Cluster compounds455TrigonalOctahed
Page 354 and 355: Cluster compoundsFig. 11.4 Closo, a
Page 356 and 357: Cluster compoundsmixture of the mor
Page 358 and 359: Cluster compoundsIt is extremely st
Page 360 and 361: Cluster compounds2- 2-~ m1 11O GQ8-
Page 362 and 363: Cluster compounds(IJ 5 -C,B,H 6 )Mn
Page 364 and 365: wUlo2-Fe(C0) 5redu cine;~C 7 H~BF4-
Page 366 and 367: Cluster compoundsdensations' do not
Page 368 and 369: Cluster compoundsA 3 A 78 78 12A 3c
Page 370 and 371: Cluster compoundsstructures of the
Page 372 and 373: Mechanisms of industrial processesT
Page 374 and 375: Table 12.2.Process Feedstock Cataly
Page 376 and 377: Mechanisms of industrial processesF
Page 378 and 379: Mechanisms of industrial processes1
Page 380 and 381: chaingrowth(alkeneinsertion)CH 3 CH
Page 382 and 383: r!~~NiJy ~ ' ,. -;,,.,~,;, ..'Ni'+2
Page 384 and 385: ţ/Ph)o-cPd =:) )cH0-C'-....Ph 2~-8
Page 386 and 387: Mechanisms of industrial processesH
Page 388 and 389: H2 C=CH2H2C=CH2[Ti]-R + C2H4coordin
Page 390 and 391: o[~] o ~ [f!- ~7:Jlinear[w]=CH~poly
Page 392 and 393: Me3 CCH2Li3HCI/WCL 6 W(=CBut)(CH2 B
Page 394 and 395: Mechanisms of industrial processesW
Page 396 and 397: Mechanisms of industrial processesT
Page 398 and 399: ••~'"'"'" 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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