Infrared in Organometallic compounds



IR is one of the first technique inorganic chemists used (since 1940) Molecular Vibration Newton¶s law of motion is used classically to calculate force constant r The basic picture : atoms (mass) are F F re

connected with bonding electrons. Re is the equilibrium distance and F: force to restore equilibrium

F(x) = -kx

where X is displacement from equilibrium

we might be able to determine the number of atoms in a group  Distinguish MX2 and MX3 groups ‡ We might distinguish monodentate from bidentate sulfate ‡ We might distinguish terminal from bridging CO ligands ‡ We can use variation in CO stretching frequency in metal carbonyl to make deduction about electronic nature of the other ligands .Analyzing inorganic molecules by IR ‡ With IR.

Stretching Frequency is lower for heavier atoms 2. Stretching Frequency vary over a narrow range for a set of related compounds .Bond Stretching Frequencies Vibration frequency of a bond depends on the mass of bonded atoms and on the force constant of the bond General Principle: 1. Stretching Frequency is lower for weaker bonds 3.

Bond Stretching Frequencies: Hydrogen Hydrogen: all bond stretch occur in the range: 4000 to 1700 cm-1 (for H-F down to H-Pb) Pb) Going down any main group in periodic table increase the mass And decrease the bond strength => Lowering stretching Frequency From Left to right along a row: the effect of increasing the mass is outweighed by the increase in Bond strenght => Frequency increase .

Bond Stretching Frequencies: Hydrogen Increase (cm-1) Decrease (cm-1) .

B- . B-O) (C.Bond Stretching Frequencies: other nuclei Stretching of bonds not involving Hydrogen are lower (below 1000 cm-1) Except for multiple bond with higher force constant Or for single bond involving nuclei in the first row (C-F.

Bond Stretching Frequencies: Carbonyl Important group of frequencies is due to Carbonyl ligand in Metal complex ‡ Terminal CO correlate with electron-righness electronof the metal ‡ Backbonding from the d-orbital of the metal to dthe T* antibonding orbital weaken CO bond => lower stretching frequency (from free CO) .

Bond Stretching Frequencies: Carbonyl Co (CO NO)(PClXPh3-X)2 CO)(NO P Table illustrating how the electronegative Chlorine on Phosphorus ligand decrease the electron density on Cobalt (central atom) Decreasing d -> p* backbonding raising CO and NO .

. the number of bands will be less than the number of ligands: some are degenerated.Patterns of group Frequencies: Carbonyl Clearly defined group frequencies like CO are very important in determining how many of the group occur in each molecule and symmetry relationship between them ‡ There is 1 stretching mode for each bond in a molecule in principle we can count the number of CO frequencies (caution as some vib. Might not be active in IR) ‡ Symmetry relating equivalent groups govern the activity of various stretching mode in IR and Raman ‡ If there is a rotation axis relating three or more CO ligands.

And Asym stretch for both groups => Therefore there are 4 CO stretch expected OC CO L OC CO M L trans-octahedral complex The 4 CO are all related by symmetry => There is only one active vibration in IR .Patterns of group Frequencies: Carbonyl L OC M CO Has only 2 CO bands: provided that the ligand preserves M(CO)3 3 fold symmetry cis-octahedral complex CO OC L OC OC CO M L The 2 CO trans to each other can be treated together The 2 CO cis to each other can be treated together There are Sym.

Group Frequencies: Type of Binding Many ligands hae different modes of binding to other atoms Terminal M CO Bridging CO M M Triple Bridge M CO M M 2130 ± 1700 cm-1 1900 ± 1780 cm-1 1900 ± 1780 cm-1 We can therefore state: CO above 1900 => terminal CO Below 1900 : Can be due to bridging CO or terminal CO with unusual reduction of CO strenght (d -> T* back bonding) .

2030. 1997. 2010 cm-1 example: only => Ru(CO)4 units held together by Ru-Ru bonds Ru- Another example: Fe3(CO)12 : CO 2040. 1840 cm-1 example: Iron complex has bridging CO as well as terminal CO .Group Frequencies: Type of Binding For example: Ru3(CO)12 : CO 2060. 2020.

g. Al2Cl6) ‡ Study compounds of known structure that has terminal M-X ‡ Study compounds that has bridging ligands From the above observations.Halogens: Type of Binding Halogens may also act as bridging/terminal ligands (e. determine the presence / absence Of bridging in a new compound .

Monothioacetate ligand Case 1 Through Oxygen only M O S CH3 O M S CH3 O M S CH3 M CH3 O Case 2 Through Sulfur (1-2 metal) (1M S Case 3 Through both Sulfur and Oxygen Case 4 Through Sulfur one M and Oxygen through other M M O CH3 M S .Polyatomic ligands: Type of Binding Polyatomic ligands can attach at different donor site.

Polyatomic ligands: Type of Binding O M S CH3 M CH3 O Case 2 M S The only one that have C=O : 1600 cm-1 S Case 1 M O CH3 The C=S : Is less characteristic: weaker and in more crowded region Band near 950 cm-1 indicate case 1 Involve chelating and bridging ligands: yield slightly reduced frequency of both stretch: ~ 1500 cm-1 for CO ~ 900 cm-1 for CS Case 3 and Case 4 .

Isotopic substitution: to interpret vibrational spectra ‡ Vibrational frequency depend on Masses of moving atoms ‡ Deuterium substitution produce large mass increase => large frequency decrease by up to 0.717 (1/¥ 2) ‡ M-H stretching decrease by several hundred cm-1 by replacing M-D ‡ This substitution can be used to remove M-H bands where they may hide other bands Example: Co(CO)4H : 4 IR bands ~ 2000 cm-1 Co(CO) Only the lowest one shift when D replace H .

Isotopic substitution: to interpret vibrational spectra Example: Co(CO)4H : 4 IR bands ~ 2000 cm-1 Co(CO) Only the lowest one shift when D replace H .

which is Cl. resolvable if the bands is narrow . the relative shift (RR is less than 0. the mass changes are small: only few cm-1 change Naturally occuring isotope mixture and isotopically enriched mixture can give useful information For Cl.Isotopic substitution: to interpret vibrational spectra For other nuclei than Hydrogen.5 ((m/m).

Isotopic substitution: to interpret vibrational spectra Isotopic substitution is most useful to identify metal-ligand metalvibrations K[OsO3N] Band just above 1000 cm-1 shift when enriching with 15N .

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