Sukaran S.


Ligand field strengths of carbon monoxide and cyanide in
octahedral coordination
Patrick Hummel, Jonas Oxgaard, William A. Goddard III, Harry Gray, J. Coord. Chem. 58 (2005) 41-45

Section 1: Brief Summary
This paper attempts at correcting one of the co-authors earlier experimental works 1 done to obtain
the ligand field splitting strength (Δ0) for metal hexacarbonyl and hexacyano complexes. The
absorption spectra of these complexes were obtained by Gray et al. over 45 years ago. In all
cases, the intense absorptions were assigned to allow metal to ligand charge transfer (MLCT)
and weaker energy bands were assigned to ligand field excitations (d-d transfers).

These assignments gave a ligand field splitting value of 35000 cm-1 (~4.35 eV) for CN-1 and 34000
cm-1 (~4.22 eV) for CO ligand.


DFT is used to calculate the ground-state energies of t2g and eg orbitals for d6 complexes V(CO)6-1. the splittings for a series of isoelectronic 3d6 complexes with CO. CN-1. 2 on M(CO)6 complexes with M = Cr. Fe(CN)6+. and Fe(CNH)62+. Mo.Sukaran S. LF splittings induced by isocyanide ligand were also calculated for V(CNH)6-1. This leads to a completely different proposal about the field strengths of carbonyl and cyanide ligands than what the co-author had concluded earlier. this issue is resolved. claiming that the stronger bands actually correspond to the LF splittings and the orbitally-forbidden MLCT bands are much lower in energy. to reexamine the previous work and to study the effects systematically. Mn(CO)6+. and CNH ligands were estimated from DFT calculations using four different exchange correlation functionals. Mn(CNH)6+. Arora 5099451 This hinted towards the argument that CN-1 is slightly stronger ligand than CO. Thus. CO(CN)63-. 2 . Cr(CO)6. However. Using DFT. W raised questions about the magnitudes of these ligand field splittings. Cr(CNH)6. Fe(CO)62+. some recent relativistic time-dependent density functional theory (TDDFT) calculations performed by Baerends et al.

BP86. JOBEX program was used to optimize geometries with generalized internal coordinates.Sukaran S. Results The obtained M-C bond distances in the complexes for the three ligands using the four different functionals are listed in a tabular form as below: The bond distances (C-X) in the ligands when complexed with the metal were also reported as follows: 3 . Semi-direct self-consistent field (DSCF) module was used to calculate ground state energies of the molecular orbitals. QZVP basis set was used for all atoms in calculating the properties of these complexes. 4 different exchange correlation functionals (B3LYP. Octahedral symmetry was assumed and m3 (triangular) grids were used. Arora 5099451 Computational Methods TURBOMOLE program package was used for ab-initio electronic structure and energy calculations. and BLYP) were used to perform 4 separate DFT calculations for each complex. PBE.

Arora 5099451 The computed N-H bond distances in the iso-cyanide complex are listed below. Discussion It is noted that for both Fe(CN)64. ligand field splitting (Δ0) from the experiments conducted earlier by the co-author was around 4.and Co(CN)63-. as stated earlier.Sukaran S. The B3LYP functional is observed to overestimate this value by 40% while other functionals underestimate the same by 10% for PBE and BP86. 20% for BLYP. The final calculated octahedral field splittings based on the energy differences of the d orbitals are also reported. 4 .3 eV.

M-C bond distance in M(CN)6 complex is much greater.Sukaran S. possibly by more than 1 eV. all the density functionals used here lead to larger values (20% more for BLYP vs 70% more for B3LYP). However. A possible rationale is that the net negative charge on the cyanide likely decreases the extent of metal back-bonding (Mπ*) compared to the other complexes. These greater bond distances further lead to lesser σ overlap. Based on these observations and taking into account their accuracy. this destabilizes the t2g orbitals. Arora 5099451 For metal carbonyl complexes. However. Gray agrees with Baerend’s results that the original assignment of the weak bands for metal hexacarbonyl complexes underestimates their field strength. a much stronger dependence of the ligand field splitting on the metal oxidation state is observed. Further arguments are made to explain the trends observed in the value of field strengths based on the metal carbon bond distances. As the oxidation state goes from negative [V(-I)] to positive [Fe(II)]. thus the claim that it is a weaker ligand than both carbonyl and iso-cyanide. 5 . For metals with same oxidation states. The eg orbitals are destabilized at the same time with the increase in sigma bonding (explained by the decrease in the M-C bond distances). Thus the effects are counter-balanced and there is no observed effect of the oxidation state. MLCT is thought to be an important factor in the strength of these metal carbon bonds. It can also be argued by looking at the computed values that the induced octahedral splitting in M(CO)6 complexes has little dependence on the metal oxidation state. Mπ* back-bonding decreases (because the nucleus exerts more attractive forces on the electrons and thus they are less soft to move over to the ligand orbitals). for the iso-cyanide (CNH) complexes. typical experimental estimate for Δ0 in octahedral symmetry is ~ 4.2eV. and the corresponding Δ0 for octahedral splitting is lower than CO and CNH. it is observed that M(CO)6 and M(CNH)6 complexes have similar ground state geometries. However.

Δ0 is much greater for V(CO)61-. while for V-1. CO derives its strength from a combination of σ donation and Mπ* back-bonding. back-bonding is very important and since carbonyl is a better π acceptor than iso-cyanide. A more general rationale for the observed differences in the ligand field strength is that regardless of the metal. 6 . an agreement is reached with Baerend’s observations and a theoretical justification based on physical arguments is provided to shed light on the relative strengths of CO and CN-1 ligands in octahedral field splittings.Sukaran S. But for V1-. so Δ0 for CN-1 and CNH will be similar. Fe(CO)62+ and Fe(CNH)62+ have comparable Δ0 in Oh field splitting. This indicates that CO is a much stronger ligand than CNH and that the relative strength of the two ligands depends on the metal in consideration. Thus. On the other hand. so M(CO)6 will have more back-bonding for any metal than M(CNH)6 complexes. CO has a larger field splitting than CNH for the vanadium complex. extent of back-bonding is small. The iso-cyanide (CNH) falls in between cyanide and carbonyl in terms of its strength as a π acceptor. For Fe(II) complexes. Arora 5099451 For Fe2+. cyanide derives most of its strength from the strong σ donation as there is little Mπ* back-bonding.

J. H. E. B. Chem. which would be consistent with the observed insensitivity of their position to the metal (as is clear from the data in Table 3). E. Snijders.. G. Am. 10356–10365. the lowest excited states in the spectra should not correspond to ligand field excitations. A. Soc. The low intensity of these shoulders.. A. Instead they should correspond to the charge transfer states. should be attributed to their forbidden nature. Chem. References (1) Gray. thus. Soc. J. 121 (44).. 2922–2927. not to their LF character. van Gisbergen. N. These low-energy shoulders should be assigned to orbitally-forbidden MLCT states. Gray et al. Baerends. This paper and its observed results and reasoning help clear this contradiction and a better understanding of the absorption spectra of transition metal complexes with carbonyl and cyanide ligands is provided. Baerends 2 in his work had noted that based on the TDDFT calculations performed by his group. J. Beach. (2) Rosa. Arora 5099451 Section 2: Improved understanding Contradicting their own work. Am. 85 (19). van Lenthe.. have performed these DFT calculations to improve upon and correct their mistake while assigning the bands observed in the absorption spectra of these metal complexes 1. A. 1963.Sukaran S.. The LF excitations should be calculated at much higher energy than what was done by Gray.. J. J. 7 . A. J. Groeneveld. S. 1999.