Table 5. Experimental and Calculated Quadrupole Splitting Parameters.
| compound | exp. |ΔEQ| (mm s–1)a | def2-TZVP |ΔEQ| (mm s–1)b | CP(PPP) |ΔEQ| (mm s–1)c | ref |
|---|---|---|---|---|
| K2[LMeFeNNFeLMe] | 2.48 | 2.37, 2.33 | 2.22, 2.18 | (15) |
| LMeFeBr(THF) | 2.36 | 2.19 | 2.34 | (16) |
| LMeFe(η6-C6H6) | 0.74 | 0.93 | 1.14 | (19) |
| MeLMe,Me2Fe | 1.80 | 1.48 | 1.69 | (19) |
| MeLMe,MeFe(Cl)2 | 1.23 | 1.00 | 1.05 | (18) |
| MeLMe,MeFe(Cl)2K(18-crown-6) | 2.10 | 2.07 | 2.27 | (17) |
| MeLMe,MeFe(μ-S)2FeMeLMe,Me | 1.14 | 1.18, 1.18 | 1.15, 1.15 | (18) |
| MeLMe,MeFe(CNXyl)3d | 0.81 | 0.76 | 0.80 | (19) |
| MeLMe,MeFe(CO)3 | 0.77 | 0.79 | 0.89 | (19) |
| LMe Fe(NCtBu)2e | 0.72 | 1.06 | 1.20 | (8c) |
| LMeFe(tBu-Py)2f | 0.59 | 0.59 | 0.56 | (8b) |
| LtBuFeCH3 | 1.74 | 2.14 | 2.10 | (21) |
| LtBuFeCl | 1.61 | 2.05 | 2.05 | (21) |
| LtBuFeNHtolylg | 1.42 | 1.72 | 1.66 | (21) |
| LtBuFe(HCCPh) | 2.05 | 2.53 | 2.44 | (21) |
| [LtBuFeH][K(18-crown-6)] | 1.84 | 2.21 | 2.25 | (8b) |
| [LtBuFeH][K(crypt)]h | 1.93 | 2.25 | 2.36 | (8b) |
| MeLMe,MeFe(η6-C6H6) | 0.69 | 0.87 | 1.08 | (19) |
| MeLMe,MeFe(η5-Ind)i | 1.07 | 1.02 | 0.89 | (22) |
| MeLMe,MeFe(Py)(μ-N2C10H10)(Py)FeMeLMe,Mej | 1.38 | 1.12, 1.10 | 1.26, 1.26 | (8e) |
| MeLMe,MeFe(Py)(μ-Py)FeMeLMe,Mej | 1.29, 1.66 | 1.14, 1.22 | 1.04, 1.37 | (8e) |
| LMeFe(AdNNNNAd)k | 1.32 | 1.53 | 1.77 | (8a) |
| LS,SFe(THF)2l | 3.77 | 3.81 | 3.99 | (23) |
| (SiPiPr3)FeCOSi(CH3)3m | 1.115 | 1.12 | 1.41 | (24) |
| Cr(iPrNPPh2)3Fe-PMe3n | 0.31 | 1.07 | 1.11 | (25) |
| [Cp*Fe(S2Ph)(N2H2)FeCp*]PF6o | 0.74 | 0.80, 0.80 | 0.82, 0.82 | (26) |
| Cp2Fep | 2.41 | 2.61 | 2.97 | (27) |
| PNPiPrFeCl2q | 2.89 | 3.25 | 3.36 | (28) |
| PNPtBuFeCl2r | 2.69 | 3.09 | 3.22 | (28) |
| [(IMes)2FeCl]s | 2.63 | 2.23 | 2.30 | (29) |
| [(IMes)(Me2-cAAC)-FeCl]s,t | 2.03 | 2.94 | 2.99 | (29) |
| [(Me2-cAAC)2-FeCl]t | 2.04 | 1.84 | 1.69 | (29) |
| [(cylDep)2Fe][BArF4]u | 5.75 | 5.43 | 5.40 | (30) |
| [(sIDep)2Fe][BArF4]v | 6.82 | 6.00 | 5.99 | (30) |
Experimentally observed quadrupole splitting.
Quadrupole splitting calculated using the def2-TZVP basis set on all atoms.
Quadrupole splitting calculated using the CP(PPP) basis set on iron.
“CNXyl” is 2,5-dimethylphenylisocyanide.
“NCtBu” is tert-butylnitrile.
“tBu-Py” is 4-tert-butylpyridine.
“NHtolyl” is 4-methylanilide.
“crypt” is 2.2.2-cryptand.
“Ind” is indenyl.
“Py” is pyridine. “N2C10H10” is 4H,4′H-[4,4′-bipyridine]-1,1′-diide.
“AdNNNNAd” is N,N‴-bis(adamantly)tetrazene.
“LS,S” is 4′,6‴-difluoro-2,2′′′′,4,4′′′′,6,6′′′′-hexaisopropyl-[1,1′,3′,1″,3″,1‴,3‴,1′′′′-quinquephenyl]-2,2′-dithiolate.
1,1′,1″-Tris(2-(diisopropylphosphino)phenyl)silane.
N-Isopropyl-1,1-diphenylphosphanamide.
Cp* is 1,2,3,4,5-pentamethylcyclopentadienyl anion. S2Ph is 1,2-benzenedithiolate.
Cp is the cyclopentadienyl anion.
Bis(2-(diisopropylphosphaneyl)ethyl)amine.
Bis(2-(di-tert-butylphosphaneyl)ethyl)amine.
IMes is 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene.
Me2-cAAC is 3,3,5,5-tetramethyl-1-(2′,6′-diisopropylphenyl)pyrrolidine-2-ylidene.
cylDep is 1,3-bis-2′6′-diethylphenyl)-4,5-(CH2)4-imidazolin-2-ylidene.
sIDep is 1,3-bis-(2′,6′-diethylphenyl)-imidazolin-2-ylidene.