Beschreibung
A very large number of organo derivatives is formed by the Group IV ele ments silicon, germanium, tin, and lead. In comparing the general properties of these elements, Table 1. 1 shows that the first ionization energies decrease (though not in a regular way) with increase in size and atomic number, con sistent with the general increase in metallic character of the elements. Electro negativity values (which have been the subject of considerable controversy) show no clear trend. Although purely inorganic compounds of tin(n) and leaden) are well known, almost all organo Group IV derivatives show an oxidation state of IV. Bonds to carbon become weaker on passing from silicon to lead, as do the element-element bonds themselves. With any particular element M (M = Si, Ge, Sn, or Pb), there is a small decrease in bond energy in the order: M-Ph > M - Me > M - Et. Although accurate data for organo derivatives are lacking, strengths of bonds to other elements probably decrease in the order: M-F> M-O > M-CI > M-H ~ M-N ~ M-S ~ M-Br > M-I, while for a particular element X, the order is: Si-X > Ge-X > Sn-X > Pb-X. It is therefore understandable that reactions leading to Si-F, Si-O, or Si-CI bonds are especially favoured in a thermodynamic sense.
Autorenporträt
InhaltsangabeGroup IV Silicon, Germanium, Tin, and Lead.- 1 Introduction.- 2 Silicon.- Tetra-alkyls and tetra-aryls of silicon.- Unsaturated organosilicon compounds.- Heterocyclic compounds of silicon and carbon.- Cyclic saturated organosilanes.- Cyclic unsaturated organosilanes.- Organosilicon(II) compounds and organosilicon radicals.- Organosilicon halogen compounds.- Monohalides, R3SiX.- Dihalides, R2SiX2.- Trihalides, RSiX3.- Organosilicon pseudohalides.- Organosilicon oxygen compounds.- Silanols.- Silanolates or siloxy-metal derivatives.- Alkoxides and aryloxides.- Siloxanes.- Silicones.- Short-lived R2Si=O intermediates.- Peroxides.- Ketones.- Organosilicon sulphur, selenium, and tellurium compounds.- Organosilicon nitrogen compounds.- Aminosilanes.- Disilazanes.- Cyclic silicon-nitrogen compounds.- Hydrazine derivatives.- Organosilylazenes.- Derivatives of hydroxylamine and amides.- Silatranes.- Organosilicon phosphorus, arsenic, antimony, and bismuth compounds.- Organosilicon hydrides.- Compounds containing silicon-silicon bonds.- Acyclic derivatives.- Cyclic derivatives.- Organosilicon-metal compounds.- Groups I and II.- Groups III and IV.- Transition-metal derivatives.- Silylmethyl-transition-metal derivatives.- 3 Germanium.- Tetra-alkyls and tetra-aryls of germanium.- Unsaturated organogermanium compounds.- Heterocyclic compounds of germanium and carbon.- Organogermanium(II) compounds and organogermanium radicals.- Organogermanium halogen compounds.- Monohalides, R3GeX.- Dihalides, R2GeX2.- Trihalides, RGeX3.- Alkylgermanes with halogenated side-chains.- Organogermanium pseudohalides.- Organogermanium oxygen compounds.- Oxides and hydroxides.- Alkoxides.- Peroxides.- Esters.- Ketones.- Organogermanium sulphur, selenium, and tellurium compounds.- Organogermanium nitrogen compounds.- Organogermanium phosphorus, arsenic, antimony, and bismuth compounds.- Organogermanium hydrides.- Compounds containing germanium-germanium bonds.- Organogermanium-metal compounds.- Alkali-metal and magnesium derivatives.- Derivatives of other main-group metals.- Transition-metal derivatives.- 4 Tin.- Tetra-alkyls and tetra-aryls of tin.- Unsaturated organotin compounds.- Heterocyclic compounds of tin and carbon.- Organotin(II) compounds and organotin radicals.- Organotin halogen compounds.- Monohalides, R3SnX.- Dihalides, R2SnX2.- Trihalides, RSnX3.- Complexes of organotin halides.- Organotin(II) halides.- Organotin pseudohalides.- Organotin oxygen compounds.- Monohydroxides and derivatives.- Alkoxy and aryloxy derivatives, R3SnOR1.- Dihydroxides and derivatives.- Tetra-alkyl distannoxanes, (XR2Sn)2O, and related derivatives.- Stannonic acids.- Peroxides.- Sn-O compounds in organic synthesis.- Organotin sulphur, selenium, and tellurium compounds.- Organotin nitrogen compounds.- Organotin phosphorus, arsenic, antimony, and bismuth compounds.- Organotin hydrides.- Hydrostannation.- Hydrostannolysis.- Use of organotin hydrides in synthesis.- Compounds containing tin-tin bonds.- Derivatives of distannane.- Derivatives of hexa-alkyl or -aryl-ditin compounds.- Derivatives of higher stannanes.- Derivatives of the type (R2Sn)n.- Organotin-metal compounds.- Alkali-metal derivatives.- Derivatives of other main-group elements.- Transition-metal derivatives.- 5 Lead.- Tetra-alkyls and tetra-aryls of lead.- Unsaturated organolead compounds.- Organolead(II) compounds and organolead radicals.- Organolead halogen compounds.- Monohalides, R3PbX.- Dihalides, R2PbX2.- Trihalides, RPbX3.- Organolead oxygen compounds.- Organolead sulphur, selenium, and tellurium compounds.- Organolead Group V compounds.- Organolead hydrides.- Compounds containing lead-lead bonds.- Dilead derivatives.- (R2Pb)x derivatives.- Organolead-metal compounds.- Alkali-metal derivatives.- Transition-metal derivatives.- References: Group IV.- V Arsenic, Antimony, and Bismuth.- 6 Introduction.- 7 Arsenic.- Tri-alkyls and tri-aryls of arsenic.- Unsaturated organoarsenic compounds.- Penta-alkyls and pen
