Coordination Compounds Part IT150 INFRARED SPECTRA Mod Be op OD ROO ooo es Taw awe Fig. I1I-1. Infrared spectra of hexammine complexes: “Teo NICs, solid tne; [chOOH,). 10, dotdaah line; [Ni(NH,) ICI, dtd line III, AMMINE, AMIDO AND RELATED, COMPLEXES (2) Ammine (NHL) Complexes Figure II-I shows the infrared spectra of some typical ammine com- plexes. Although the structure of the ammine complex as a whole is highly complicated, the vibrational spectrum may be understood if simple 1: 7 model (ie, M—NH,) is used. The normal niodes of vibration of such a simple model may be represented by those ofa tetrahedral ZXY molecule, shown in Fig. III-2. Thus the following six vibrations are expected for the nia) thy) - & Fig. IT-2. Normal modes of vibration of tetrahedral ZXY, molecule. (The band assgn- ment is given for an M—NH, group) SeerP sec, TII-1 COORDINATION COMPOUNDS 151 1:1 complex model: antisymmetric and symmetric NH, stretching, Nii, degenerate deformation, NH, symmetric deformation, NH, rocking and MEN stcetching. According tothe selection rule forthe point group Cs, these vibrations are both infrared and Raman active. Of these six vibrations, the NH, stretching bands can be assigned empirically since they always appear between 3400 and 3000 cm". The three bending modes were Ast assigned by Nakagawa and Mizushima! from a normal coordinate analysis based on a 1:1 complex model ike that in Fig. 1-2 (®) NH, Stretching Bands Table III-Ilists the vibrational frequencies of typical ammine complexes. ‘The NH, stretching bands in the complexes are usually broader, and their frequencies lower, than those of the free NH, molecule. Several factors Tone H1 RATIONAL FREQUENCIES OF TYPICAL AMMINE ‘Comtexes (cm)? ‘Compound NHS) SANE) 80H) pNH) NHS 3414,3336 1628950 - (NINH NCIOD, | 3397,3312 16181268620) [CrONHS).HCIO.), | 3330,3280 16021384718 [CotNH)6ICI0. | 3320,3240 1601352803 [CO(NH).KNO.)s | 3290,3200 1618 = = [CONE Ils 3150 1390 1323792. (CONE) IB 3120 13781318797 (CONE) -ICI5 3070 1031325 INHAJCI 3138,3041 7101403 - may be responsible for the frequency shift. One is the effect of coordina- tion? ‘The NHy stretching frequency decreases in the series NH > [NiQNHL)6}?* > [Cr(NH,)g}?* > [Co(NH,)6]°* > [NH¢]*, if the perchlo- rates are compared. On the other hand, the stability order of these com- pounds is known to be Co(II1) > Cr(I) > Nit). Therefore it is reasonable to conclude, that the N—H bond order decreases (and the NH stretching frequency decreases) as the M—N bond order increases in the stability order ‘mentioned. Since the NH, stretching frequencies of the ammine complexes are intermediate between those of free NH, and the [NH,]* ion, the M—N bond of the ammine complexes is partially ionic. ‘The NH; stretching frequency is also sensitive to changes in the anion. AAs seen in Table I1I-l, the frequency of the NH, stretching band of the [Co(NH,)«]?* ion decreases by about 230 cm"? when (ClO,}” ig replaced by C1”. There is ample evidence of the presence of hydrogen ‘bonding between the NH of ammine complex ions and anions such as halogens.*