Metal-cyclopentadienyl complexes

CHEM311/313

Conjugated dienes - bonding

In conjugated dienes/polyenes the bonding of the entire conjugated unit must be considered “as one”.

the C=C bonds cannot be treated as separate units.

Donation can occur

from the diene HOMO to an empty metal orbital from a full d-orbital to the LUMO of the diene

B2 p 15-17

Donation from the HOMO • Strong -donation from 2 to the metal • C-C anti-bonding depopulates C1=C2 bond • weaker. shorter • depopulates C2=C3 anti-bond • • all bonds same length • di-ene type structures with weakened C=C • B2 p 16 . longer stronger.

Back-donation into the LUMO  electrons flow from metal dxz-orbital into 3    M C1-C2 anti-bonding C2-C3 bonding C3-C4 anti-bonding C-C bonding  bond lengths   long-short-long metallacycle B2 p 16 .

of electrons donated = the number of -electrons The ligand occupies (no. of electrons donated)/2 co-ordination sites . The no.Aromatic polyolefins    If the olefin is aromatic then the -cloud can co-ordinate.

Cyclopentadienide   C5H5 (Cp) has 6 -electrons ferrocene is its archetypical complex _ 2+ vs  Large family of metallocene complexes .

Synthesis of cyclopentadienyl compounds Co Co2+ heat 2 Na 2 Na Fe2+ Fe MCl4 Cl M Cl .

B1 p. are in the “wrong” place.MO picture of the bonding     a1 ligand orbital has correct symmetry to interact with dz2 but lie on the dz2 nodal plane. i.e. 46-47 http://www.html . e2g ligand orbitals can overlap with the metal dx2-y2 and dxy but the degree of overlap is not large so these MOs are essentially non-bonding. e1u interaction between the metal px and py also gives some stabilization. e1g ligand set overlaps with the metal dxz and dyz orbitals forming a strong set of -bonds.ilpi.com/organomet/cp.

ie/cryst/oscail_tutorial/moilin/ferrocene/ferrocene.Simplified MOs for eclipsed conformation a1g overlap weak e1g overlap strong http://www.nuigalway.htm but watch out for the typos! .

MO diagram Fe(II) d6 ion  6 metal d electrons  12 electrons donated by the 2 Cp ligands .

Ferrocene and 18 electron rule  Lowest MOs are the 6 ligand to metal bonding orbitals – ligand based There are 3 weakly bonding.g. ferrocene is readily oxidized to [(Cp)2Fe]+  Sandwich complexes with 15 to 20 valence electrons are known (vide infra) . or non-bonding metal based orbitals next in energy 18 electrons are needed to fill all 9 orbitals above BUT. no strong NEED to fill the non-bonding MOs     e.

Metallocenes & redox  electrons are easily removed from/added to the HOMO/LUMO metallocenes are mild oxidizing/reducing agents can be used as electron transfer catalysts    ExacTech pen meter .

Sandwich compounds      metal based HOMOs & LUMO are essentially non-bonding no NEED to fill HOMOs small penalty on filling the LUMO 6 L M bonding orbitals must be filled (12 electrons) total electron counts from 15 – 20 are known 6 L M bonding MOs B2 p 47 .

H&S p 731 .ExacTech pen meter B2 p 51.

Reaction at the ring or metal H&S p 732 .

Ring whizzer  staggered and eclipsed conformations have very similar energies and MOs. even if the metal environment makes the ring carbons inequivalent .  1H and 13C{1H} NMR spectra usually show a single resonance even at low T.

Ring whizzer  a1 orbital contributes a small “nondirectional” component to the bonding C5H5 fragment can spin like a plate on a stick Unlikely to be explanation. since the e1g overlaps are strongly bonding   .

Ring whizzer  Unlikely to be explanation. Small barrier to overlaps “hopping around the ring C5H5 fragment can spin like a plate on a stick    http://alpha.umb.edu/chemistry/ch612/documents/ConstructingpiMOdiagramssandwichcomplexes.pdf . since the e1g overlaps are strongly bonding Overlaps are maintained as conformation changes from staggered to eclipsed.chem.

Rare example of inequivalence in the NMR spectra  steric hinderance between the phenyl group and the Cp protons allows the ring whizzing to be frozen out at -100 oC separate resonances are observed for each carbon atom of Cp H Ph H Os PPh3 PPh3  .

Other bonding modes for cyclopentadiene  cyclopentadiene can also behave as an alkyl ligand or as an 3 ligand .

Ring slippage changes electron count at metal  loss of aromaticity  no reaction  redistribution of aromaticity  reaction goes B2 p 61 .

Many metal-arene complexes known  Benzene and its derivatives have similar frontier orbitals and same number of valence electrons as CpSimilar complexes are known Similar redox and magnetic properties Similar reactivity    B2 p 76 .

Synthesis B2 p 75 .

cf Reactivity at the ring in arenes  reactivity mirrors that of Cp in ferrocene - B2 p 79 .

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