11/9/15. Intermolecular hydrogen bond: Hydrogen bond: Intramolecular hydrogen bond: Induced dipole moment, polarisability
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1 Induced dipole moment, polarisability in electric field: Van der Waals forces Intermolecular forces other than covalent bonds or other than electrostatic interactions of ions induced d. moment µ * = α E E electric filed intensity (strength) α polarisability (C 2 m 2 J -1 ) polarisable volume (m 3 ) Also polar molecules can be additionally polarised Johannes van der Waals Dutch, Nobel Prize-1910, Physics interactions: Electrostatic: ion-ion; ion-dipole vdw: dipole-dipole dipole-induced dipole induced dipole-induced dipole + higher multipoles ~ kj/mol 2 Hydrogen bond: Intermolecular hydrogen bond: atractive interaction of a (bond) hydrogen atom with an electronegative atom (N, O, F) of a different bond δ - δ + - stronger than v. d. Waals - weaker than a covalent or ionic - directional Dimers of carboxylic acids Bond energy: ~ x10 2 kj/mol Intramolecular hydrogen bond: electronegative atom donates an lone pair 3 acetylacetone 4 1
2 Typical energies and lengths of hydrogen bonds: σ-hole bond : With elements of groups F H... :F 155 kj/mol (40 kcal/mol) O H... :N 29 kj/mol (6.9 kcal/mol) O H... :O 21 kj/mol (5.0 kcal/mol) N H... :N 13 kj/mol (3.1 kcal/mol) N H... :O 8 kj/mol (1.9 kcal/mol) Polarizácia X H + counter-intuitive bond, energies similar as for H-onds Halogen bond X H... Y h. bond donor h. bond acceptor length/pm ~110 ~ σ-hole 6 σ-hole bonding - X Gr. 17 -halogen bond (F, Cl, Br, I) = E Gr chalcogen bond (S, Se, Te) Pn Gr pnictogen bond (P, As, Sb) - T Gr tetrel bond (Si, Ge, Sn) - A Gr. 18 aerogen bond (Kr, Xe) σ-hole dictates the bond direction SbCl 3 hexamethylbenzene E -57 kj/mol AsCl kj/mol. 8 2
3 Coordination compounds (complex) Coordination compounds (complex) complex: used by chemists for compounds that consist of (several) other compounds that can exist separately coordination sphere (inner) No. of donors exceeds the value of oxidation number Lewis acid central atom acceptor donor ligands 9 usually (poly-nuclear) ions + counterions Lewis base 10 Some of further basic concepts chelate complexes Ligands: monodentate a single donor atom (H 2 O, CN -, F - ) polydentate their geometry enables to occupy (bi-, tri-...) more than a single coordination position several donor atoms (chelate agents) (e.g. ethylendiamin H 2 N-CH 2 -CH 2 -NH 2 ) Ethylendiamin (en) EDTA Ethylendiamintetraacetate(4-) Coordination number: number of donor atoms coordinated in the inner sphere bridging ligands
![cis-[ptcl2(nh3)2]](/docs-images/75/72850804/images/4-7.jpg "trans-[ptcl2(nh3)2]")
4 11/9/15 Typical space structures of complexes Coordination compounds: bonds/structure Alfred Werner, Swiss, , Nobel Prize 1913 Showed that transition metals create complexes with square, tertrahedral, octahedral structure transcisgeometrical isomers e.g. cis-[ptcl2(nh3)2] trans-[ptcl2(nh3)2] diammin-dichloridoplatinum(ii) complex Trigonálny dodekaéder Trojnásobne zastrešená trigonálna prizma Coordination compounds: bonds/structure Geometrical isomerism for octahedral structures Valence bond theory with hybrid AO in most cases enables explanation of the structure cis- trans- mer- coord. No. form of coord. sphere examples 2 SP linear [CuCl2]- [Ag(S2O3)2]3- fac- Info: Optical isomerism: mirror image enatiomers 4 SP3 D3S tetrahedron [Co(NCS)4]2- [NiCl4]2[BF3(NH3)] 4 DSP2 SP2D square [Mn(H2O)4]2+ [PdCl4]2[Pd(NH3)4] 2+ Ni(CN)4]2-6 D2SP3 SP3D2 chirality, chiral molecules 15 octahedron [Fe(H2O)6]2+ [Fe(CN)6]3- [FeF6]3[PdCl6]216 4
![paramagnetic [NiCl 4 ] 2- unpaired electrons diamagnetic [Ni(CN) 4 ] 2- paired electrons Ni(II) -[NiCl 4 ] 2](/docs-images/75/72850804/images/5-0.jpg "Ni(II) -[Ni(CN) 4 ] 2 High-spin complex sp 3 valence Ni 2+ dsp 2 Ni 2+ 28Ni 3d 4s 4p Ni 2+ Ni Low-spin complex 3d")
5 paramagnetic [NiCl 4 ] 2- unpaired electrons diamagnetic [Ni(CN) 4 ] 2- paired electrons Ni(II) -[NiCl 4 ] 2 Ni(II) -[Ni(CN) 4 ] 2 High-spin complex sp 3 valence Ni 2+ dsp 2 Ni 2+ 28Ni 3d 4s 4p Ni 2+ Ni Low-spin complex 3d 4s 4p Coordination compounds: bonds/structure?????? metal-ligand bond is weaker than usual covalent b. Crystal field theory Central atom in electrostatic field of (ionic) ligands (as point charges) (electrostatic theory of ligand field) Splitting of d levels: octahedral complex Some complexes use inner d orbitals others use outer d orbitals Ligand field Transition metal complexes use to be intensively colored MO theory simplified approximations d
![[Fe(CN) 6 ] 3- [FeF 6 ] 3- Relative](/docs-images/75/72850804/images/6-8.jpg "ligand field strengths [Fe(CN) 6 ]")
![3- [FeF 6 ] 3- e g Low-spin](/docs-images/75/72850804/images/6-9.jpg "complexes High-spin complexes t 2g")
6 Why the transition metal complexes are colored? octahedral e g t 2g complex is violet d-d transitions splitting of d levels: tetrahedral complex d e t 2 21 low and high-spin complexes [Fe(CN) 6 ] 3- [FeF 6 ] 3- Relative ligand field strengths [Fe(CN) 6 ] 3- [FeF 6 ] 3- e g Low-spin complexes High-spin complexes t 2g Fe 3+ Fe 0 5d 4s Spectrochemical series
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