Octahedral ML6 π Complexes

MIT OpenCourseWarehttp://ocw.mit.edu 5.04 Principles of Inorganic Chemistry II �� Fall 2008 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms. 5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera Lecture 13: Octahedral ML6 π Complexes The basis set needs to be expanded for metal complexes with ligands containing π-orbitals. An appropriate basis for ligands with two orthogonal π orbitals, e.g. CO, CN–, O2–, X–, to the σ bond is shown below, The arrow is indicative of the directional phase of the pπ orbitals. Owing to their ungerade symmetry, in constructing the pπ representation • a p orbital, i.e. arrow, that transforms into itself contributes +1 a p orbital that transforms into minus itself contributes –1 a p orbital that moves, contributes 0 E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh6σdOh 6002200042 → a1g + t1u + egΓσ 120 0 0–4 0 0 0 00 → t1g + t1u + t2g + t2uΓπ There is a second method to derive the pπ basis. The Cartesian coordinate systems on each ligand contains the σ and π basis sets. Thus the Γx,y,z irreducible representation (which is the sum of Γx + Γy + Γz or Γz + Γx,y for irreducible representations for which x,y,z are not triply degenerate) defines the 1σ and 2pπ bonds of each ligand. Since the bond is coincident with the ligand, an unmoved atom is approximated by Γσ. On the basis of geometrical considerations, the following is true, Γ unmoved = ΓσatomsΓσ+π = Γx,y,z • Γσ Γπ = Γσ+π – Γσ 5.04, Principles of Inorganic Chemistry II Lecture 13 Prof. Daniel G. Nocera Page 1 of 4 Oh Γσ T1u = Γx,y,z Γσ+π E 6 3 18 8C3 6C2 0 0 0 –1 0 0 Γσ+π =6C4 3C2 i 6S4 8S6 3σh 2 2 0 0 0 4 1 –1 –3 –1 0 1 2 –2 0 0 0 4 a1g + eg + t1g+ 2t1u + t2g + t2u 6σd 2 → a1g + t1u + eg 1 2 → a1g + eg + t1g + 2t1u + t2g + t2u Γσ = a1g + t1u + eg Γπ = Γσ+π – Γσ = t1g + t1u + t2g + t2u The σ SALCs have already been derived in Lecture 12. Methods 1-3 of Lecture 12 can be employed to determine the pπ SALCs. For the orbitals that transform as t1u and t2g, Method 3 (mirror the metal atomic orbital symmetry) is convenient. For the t1u SALC, and 2 others (in the xz and yz planes as defined by the symmetries of the py and px orbitals) pz ψ t(11u) = 1 ( Lπ3 + Lπ 4 + Lπ5 + Lπ6 )2 The t2g SALCs have the mirrored symmetry of the (dxy,dxz,dyz) orbital set, and 2 others (in the xy and xz planes as defined by the symmetries of the dxy and dxz orbitals) dyz ψ t(21g) = 12 ( Lπ1 − Lπ2 − Lπ4 + Lπ6 ) Non-bonding SALCs must be ascertained from projection operators and Schmidt orthogonalization methods. 5.04, Principles of Inorganic Chemistry II Lecture 13 Prof. Daniel G. Nocera Page 2 of 4 For a π donor complex such as CoF63–, t1u M–L and M–L 3.7 eV see VOIE 4p a1g M–L note, the energy gap is small enough that this molecule is high spin 7.3 eV 4s see VOIE eg t2g M–L (dx2–y2,dz2) decreased energy gap (relative to -only case) owing to participation M–L (dxz,dyz,dxy) of t2g orbitals in M-L antibond 9.4 eV 3d see VOIE n.b t1g,t2u t1u eg a1g 6F– F p orbitals, these are all 12L degenerate at ~18.6 eV see VOIE of F, offset to (M-L )t1u reduce congestion arising from 18 orbitals 6L (M-L )t2g at the same energy M–L formed from pz, the s orbital on F too low in energy to participate in M-L bonding (VOIE = 40 eV) Co3+CoF63–5.04, Principles of Inorganic Chemistry II Lecture 13 Prof. Daniel G. Nocera Page 3 of 4 For a π-accepting ligand set, orbitals have the same form (or symmetry) as π donors, t1u t2g 11⎛⎜⎝Lπ3 ⎞⎟⎠ψ⎛⎜⎝Lπ⎞⎟⎠**** ****(1) (1)ψππππππLLL− L− LL++++==4 5 6 1 2 4 6t1u t222g The only difference between the π-donor and π-acceptor MO diagrams is the relative placement of the π* orbitals relative to the metal atomic orbitals; for Co(CN)63–, t1u M–L and M–L 3.7 eV 4psee VOIE 7.3 eV a1g eg M–L (dxzt1u eg a1g t2g M–L M–L M–L (dx2–y2,dz2) n.b t1g,t2u (M-L )t1u (M-L *) t2g Co3+ 6CN– Co(CN)6 3– increased energy gap (relative to -only case) owing to participation 9.4 eV 3d of t2g orbitals in M-L see VOIE bond 12L *4s see VOIE ,dyz,dxy) thelonepairHOMO of 6L CO, PES spectrum sets the energies of these orbitals at 14 eV 5.04, Principles of Inorganic Chemistry II Lecture 13 Prof. Daniel G. Nocera Page 4 of 4