The document discusses various classes of main group organometallic compounds, including their classification, formation of metal-carbon bonds, and properties. It focuses on lower alkyl derivatives of group 1 metals like lithium, as well as Grignard reagents which are important organometallic compounds used in organic synthesis. Organometallic compounds of groups 2 and 14 are also briefly described.
The document discusses various classes of main group organometallic compounds, including their classification, formation of metal-carbon bonds, and properties. It focuses on lower alkyl derivatives of group 1 metals like lithium, as well as Grignard reagents which are important organometallic compounds used in organic synthesis. Organometallic compounds of groups 2 and 14 are also briefly described.
The document discusses various classes of main group organometallic compounds, including their classification, formation of metal-carbon bonds, and properties. It focuses on lower alkyl derivatives of group 1 metals like lithium, as well as Grignard reagents which are important organometallic compounds used in organic synthesis. Organometallic compounds of groups 2 and 14 are also briefly described.
The document discusses various classes of main group organometallic compounds, including their classification, formation of metal-carbon bonds, and properties. It focuses on lower alkyl derivatives of group 1 metals like lithium, as well as Grignard reagents which are important organometallic compounds used in organic synthesis. Organometallic compounds of groups 2 and 14 are also briefly described.
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Main Group Organometallic Compounds
Outline Classification of organometallic compounds Formation of M-C bonds and their stability to hydrolysis and oxidation Structure and properties of lower alkyls of group 1 metals, beryllium and boron Synthesis, structure and reactions of Grignard reagents Properties and uses of group 14 organometallic compounds
References P. Powell, Principles of Organometallic Chemistry, 2nd ed., Chapman and Hall G. Wilkinson, F. Stone, E. Abel, Comprehensive Organometallic Chemistry, Vol. 1 http://web.chemistry.gatech.edu/~wilkinson/Class_notes/CHEM_3111_6170/Main_group_organometallics.pdf http://www.cem.msu.edu/~reusch/VirtualText/orgmetal.htm
Organometallic Compounds Definition compounds containing metal-carbon bonds M+C May include B, Si, Ge, As, Sb, Se, Te Exist at ordinary temperatures as low melting crystals, liquids or gases Commonly soluble in weakly polar organic solvents eg. toluene, ethers, alcohols Variable chemical properties
Classification Based on type of metal-carbon bond Ionic most electropositive elements Covalent electron deficient: metals with less than half filled valency shells, form strongly polarizing cations electron precise electron rich
Ionic Covalent: metals that have a strong tendency to form alkyl or aryl bridged species Covalent: Elements that form volatile covalent organo derivatives In general, the reactivity parallels the ionic character of the C-M bond
Classes of Organometallic Compounds
Ionic M+R- highly electropositive metals very reactive high mpt. low volatility Low or negligible solubilities in non-polar, non coordinating solvents
Classes of Organometallic Compounds
Highly polar, covalent Li, Al alkyls, Grignard reagents Polarity is a source of reactivity Adopt associated structures bonding power of electron pairs spread over more than 2 atoms
Classes of Organometallic Compounds
Slightly polar covalent less electropositive elements Behave like organic compounds Low mpt. Volatile Soluble in non-polar solvents
Stability of Organometallic Compounds
Oxidation All organometallic compounds are thermodynamically unstable to oxidation Due to large negative free energies of formation of metal oxide, carbon dioxide and water
Many kinetically unstable to oxidation at or below room temperature
Associated with the presence of empty low lying orbitals on the metal atom, or a non bonding pair of electrons
Stability of Organometallic Compounds
Hydrolysis Involves nucleophilic attack by water Facilitated by the presence of empty low lying orbitals on the metal atom which can accept electrons Organometallic compounds of Gps 1, 2, Zn, Cd, Al, Ga, In readily hydrolysed Rate of hydrolysis is dependent on M-C bond polarity greater polarity, faster rate Alkyls and Aryls of groups 14 and 15 are kinetically inert to hydrolysis by water because the metal atoms are surrounded by a filled shell of 8 electrons. Nucleophilic attack is no longer favoured
Main Group Metal-Carbon Bond Formation
Reaction of metal with organic halogen compounds 2M + nRX RnM + MXn (or RxMXy where x+y=n)
Reaction driven by exothermic formation of the metal halide Suitable for synthesis of organometallic compounds of the most electropositive elements
Main Group Metal-Carbon Bond Formation
Metal exchange M + RM RM + M Dependent on the difference in free energies of formation of the two species RM and RM Endothermic or weakly exothermic organometallic compounds should be the most versatile reagents RM in such reactions (ie compounds of Hg, Tl, Pb, Bi)
Main Group Metal-Carbon Bond Formation
Reactions of organometallic compounds with metal halides RM + MX RM + MX Most widely used and versatile of all laboratory methods Organolithium and Grignard reagents most commonly used
Main Group Metal-Carbon Bond Formation
Insertion of alkenes and alkynes into metal or nonmetal hydride bonds Hydroboration RCH=CH2 + HB RCH2CH2B
Other insertion reactions Addition of a species A-B to an unsaturated system X=Y or XY A-B + X=Y A-X-Y-B
A = metal atom B= C
Hal
Metal
Organometallic Compounds of Group 1
Highly reactive Reacts readily with oxygen (all traces of oxygen must be excluded when considering other reactions) Some ionic, some covalent Reactivity of heavier alkali metals due to negative charge on C atom
Organometallic Compounds of Group 1
Methyl, ethyl and phenyl derivatives ignite in air Potassium and sodium compounds more easily oxidized than lithium analogues For oxidation of alkyl compounds: RM + O2 RO2M RO2M + RM 2ROM
Organometallic Compounds of Group 1
Protonation and Hydrolytic Stability Readily hydrolysed React readily with a variety of proton sources to give the hydrocarbon RH Deprotonate solvents, ethers in particular Et2O + RLi RH + CH2=CH2 + LiOCH2CH3
Organolithium Compounds Small size and polarizing power of Li+ causes its compounds to have more covalent character than other group members Organolithium compounds more stable and less reactive than other organocompounds of group 1 Due to lower polarity
Valuable in chemical synthesis due to: High reactivity Relatively easy preparation Solubility in inert solvents Used for the same kinds of synthesis as Grignard reagents
Organolithium Compounds Polar character causes strong association Geometry of coordination sphere is determined by steric effects (as in ionic structures) rather than interaction of electron pairs. Eg. Methyllithium consists of tetrameric aggregates in solid state and in solution Li4(CH3)4
Lithium Organometallics Lithium alkyls Extremely reactive Sensitive to oxygen and moisture Dry apparatus and solvents must be used Air must be excluded (reactions carried out under argon or nitrogen
Lithium Organometallics Preparation Lithium metal with alkyl halide 2Li + RX LiX + RLi Physical state of Li important any coating must be removed (oil coating removed by washing in hexane under inert atmosphere
Convenient route to vinyl and allyllithium compounds
4PhLi + (H2C=CH)4Sn 4H2C=CHLi + Ph4Sn
Lithium Organometallics Preparation Metal hydrogen exchange (metallation) PhLi + O O Li + C6H6
Believed to involve nucleophilic attack on the acidic H atom Metal halogen exchange (halide abstraction) RLi + PhI RI + PhLi
Organolithium Reactivity Nucleophilic attack on multiple bonds RLi + RCCH LiCCR React with aldehydes and ketones to form alcohols RLi + RCHO + H2O RCH(OH)R + LiOH Carboxylic acid salts and acid chlorides to form ketones (after hydrolysis)
Organic groups have considerable carbanionic behaviour Extremely reactive Paraffin hydrocarbons are the most suitable reaction media (ethers are cleaved, aromatic hydrocarbons metallated)
Organosodium and potassium compounds
Preparation Mercury alkyl method 2Na (excess) + HgR2 2RNa +Hg, Na (amalgam) Exchange between sodium or potassium tert-butoxide and organolithium (in paraffinic solvent) RLi + ButONa RNa + LiOBut Direct reaction between the metals and alkyl or aryl halides is complicated by exchange and coupling reactions which lead to mixtures Exception: 3 C5H6 + 2Na 2C5H5-Na+ + C5H8
Group 2 Organometals Be, Mg form covalent compounds highly reactive resemble organolithium compounds Ca, Sr, Ba Ionic Few compounds
Organoberyllium Compounds Be2+ - High polarizing power covalent compounds Coordination number up to 4 known CN = 2 use of sp hybrid orbitals, linear compounds eg. But2Be CN = 3 sp2 orbitals, eg. Me2BeNMe3, rare CN = 4 sp3 orbitals, tetrahedral bonding, common Limited study due to high toxicity of Be compounds and air sensitivity of organometallic derivatives
Organoberyllium Compounds Solids or liquids Air sensitive React with Lewis bases, protic acids Form polymeric species (extent of association dependent on steric requirements of the organic group)
Organoberyllium Compounds - Structure
Me Be Me Me Be n
* Be *
Me
* Et Be
Et Be Et Et
Dimethylberyllium - polymeric
Diethylberyllium - dimeric
Me3C
Be
CMe3
Di-tert-butylberyllium - monomeric
Dimethylberyllium Colourless needles Polymeric Be sp3 hybridized, C sp3 hybridized 3 centre, 2 electron bonds formed Only soluble in solvents which are sufficiently strong donors to break down polymeric structures eg. Insoluble in benzene, monomeric in ether
Grignard Reagents Alkyl or aryl magnesium halides RMgX Most important organometallic compounds Commonly used in organic and inorganic synthesis Act as nucleophiles React readily with protic solvents and compounds with acidic protons
Grignard Reagents - Synthesis
Action of alkyl or aryl halide on Mg RX + Mg RMgX Must be carried out in absence of moisture and oxygen polar aprotic solvent eg. diethyl ether or THF; inert atmosphere
Reactivity of RX with Mg: I > Br > Cl > F Monomeric species exist in dilute solutions and in strong donor solvents In diethyl ether at high Mg concentrations, polymeric species exist Structure normally includes the solvent
Grignard Reagents Solution equilibria Variety of species present in solution Equilibria position dependent on Steric and electronic nature of alkyl or aryl group Nature of the halogen (size, electron donor power) Nature of the solvent Concentration Temperature Presence of impurities
Reactions Reaction with acid RMgX + HX RH + MgX2 Reaction with halogen RMgX + X2 RX + MgX2 Reactions with halides RMgX + BCl3 BR3 RMgX + SnCl4 SnR4
Reactions Reactions with ketones & CO2 RMgX + H2C=O +H2O RCH2OH RMgX + RHC=O +H2O RRCHOH RMgX + R2C=O +H2O R2RCOH RMgX + CO2 + H+ RCOOH
Organoboron Trialkyl and triarylboranes Monomeric too much crowding around B atom for polymerisation Preparation Reaction of organolithium, Grignard or organoaluminum reagents on borate esters or the ether complex of BF3 B(OMe)3 + 3RMgX R3B + 3Mg(OMe)X 3CH3MgI + BF3 (CH3)3B Hydroboration RCH=CH2 + HB RCH2CH2B
Organoaluminum Trialkyls and triaryls Highly reactive Colourless Volatile liquids or low melting solids Ignite spontaneously in air React violently with water Dimeric Me Al Me Me Me Al Me Me
Organoaluminum AlR3 (Al2R6) react readily with ligands to form adducts LAlR3 Al2Me6 + 2NEt3 2Me3AlNEt3 Stronger Lewis acids than organoboron compounds React with protonic reagents to liberate alkanes Al2R6 + 6HX 6RH + 2 AlX3 (X = OH, OR, Cl, Br) Reactions with halides or alkoxides of less electropositive elements produces other organometallics MXn +AlR3 (excess) MRn + n/3AlX3 (M = B, Ga, Si, Ge, Sn, etc.)
Organoaluminum Main importance stems from alkene insertion reactions Alkenes insert into the Al-C bonds of AlR3 at 150o and 100atm to give long chain derivatives
Al
H2C=CH2
C2H4 Al CH2CH2R
Al (CH2CH2)2R C2H4 (CH2CH2)nR
Al
Group 14 Organometals Silicon Organosilicon compounds prepared by: Reaction of SiCl4 with organolithium, Grignard reagents or organoaluminum compounds Hydrosilation of alkenes Direct reaction of RX with Si in the presence of a Cu catalyst Cu powder 2MeCl + Si Me2SiCl 300o
Organosilicon Compounds Form polymers under hydrolytic conditions Ph2SiCl2 Ph2Si(OH)2 1/n (Ph2SiO)n + H2O H2O > 100o
Organotin Compounds SnX4-nRn X = Cl, F, O, OH, n = 1 - 4 For commercial applications, R is usually a butyl, octyl or phenyl group Mono, di, tri and tetrasubstituted compounds are widely used
Organotin Compounds - Applications
Monosubstituted compounds RSnX3 PVC stabilizers
Disubstituted R2SnX2 Plastics industry as stabilizers (PVC) Catalysts in production of urethane foam Room temperature vulcanization of silicones
Department of Chemistry, Ben-Gurion University of The Negev, Beer-Sheva, Israel Department of Biological Chemistry, The College of Judea and Samaria, Ariel, Israel
Department of Chemistry, Ben-Gurion University of The Negev, Beer-Sheva, Israel Department of Biological Chemistry, The College of Judea and Samaria, Ariel, Israel
