Coordination Chemistry شیمی کوئوردیناسیون. Alireza Gorji Department of Chemistry, Yazd University. Coordination Chemistry
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1 26 Coordination Chemistry شیمی کوئوردیناسیون Alireza Gorji Department of Chemistry, Yazd University Mortimer, C.E.; Müller, U. Chemie 10 th Ed. Stuttgart Coordination Chemistry Alfred Werner Nobel prize
2 20_432 فلزات واسطه Transition Metals d-block transition elements Sc Ti V Cr Mn Fe Co Ni Cu Zn Y Zr Nb Mo Tc Ru Rh Pd Ag Cd La* Hf Ta W Re Os Ir Pt Au Hg Ac Unq Unp Unh Uns Uno Une Uun Uuu f-block transition elemen ts *Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 3 4 2
3 5 Coordination compounds Complexes Lewis base B Ligand (nutral molecule or ion) Lewis acid A Metal atom or Metal ion A + :B A-B 6 3
4 Terminology for Complexes complex central atom ligands coordination number 7 کمپلکس های چهاروجهی 8 4
5 کمپلکس های مسطح مربع 9 Coordination Number: 5 Coordination Number:
6 N NH NH N 11 Myoglobin 12 6
7 Coordination Environment of Fe 2+ in Oxymyoglobin and Oxyhemoglobin
8 نامگذاری 15 نامگذاری Ligands Monodentate Multidentate Bidentate Tridentate Tetradentate 16 8
9
10 Transition Metal Name if in Cationic Complex Name if in Anionic Complex Sc scandium scandate Ti titanium titanate V vanadium vanadate Cr chromium chromate Mn manganese manganate Fe iron ferrate Co cobalt cobaltate Ni nickel nickelate Cu copper cuprate Zn zinc zincate 19 Nomenclature of Coordination Complexes [Ag(NH 3 ) 2 ]Cl diamminesilver(i) chloride K 3 [Fe(CN) 6 ] potassium hexacyanoferrate(iii) [Cu(NH 3 ) 4 ]SO 4 tetraamminecopper(ii) sulfate [Co(NH 3 ) 6 ]Cl 3 hexaamminecobalt(iii) chloride 2 di bis 6 hexa hexakis 3 Tri tris 7 hepta heptakis 4 tetra tetrakis 8 octa octakis 5 penta pentakis 9 nona nonakis 10 deca decakis [Co(en) 2 Cl 2 ]F dichlorobis(ethylenediamine)cobalt(iii) fluoride [Fe(bipy) 3 ]Cl 2 tris(bipyridine)iron(ii) chloride 20 10
11 [Co(NH 3 ) 4 Cl 2 ] + tetraamminedichlorocobalt(iii) ion [Pt(NH 3 )BrCl(CH 3 NH 2 )] amminebromochloromet hylamineplatinum(ii) [Pt(NH 3 ) 4 ] 2+ tetraammineplatinum(ii) ion [PtCl 4 ] 2- tetrachloroplatinate(ii) ion [PtCl 6 ] 2- hexachloroplatinate(iv) ion Isomer designations come before the rest of the name and in italics cis-diamminedichloroplatinum(ii) trans-diamminedichloroplatinum(ii) 21 K 2 [Co(NH 3 ) 2 Cl 4 ] potassium diamminetetrachlorocobaltate(ii) [Co(NH 3 ) 4 Cl 2 ]Cl tetraamminedichlorocobalt(iii) chloride [Co(NH 3 ) 4 Cl 2 ] + tetraamminedichlorocobalt(iii) ion [Ti(H 2 O) 6 ][CoCl 6 ] hexaaquatitanium(iii)hexachlorocobaltate(iii) 22 11
12 K 3 [Fe(CN) 6 ] potassium hexacyanoferrate(iii) [Fe(CN) 6 ] 3- hexacyanoferrate(iii) ion [Co(NH 3 ) 6 ] 3+ [Fe(SCN) 6 ] 3- [Co(en) 3 ] 3+ [Cr(C 2 O 4 ) 3 ] 3- [Fe(EDTA)] -1 [Co(EDTA)] _441 ایزومری Isomerism Isomers (same formula but different properties) Structural isomers (different bonds) Stereoisomers (same bonds, different spatial arrangements) Coordination isomerism Linkage isomerism Geometric (cis-trans) isomerism Optical isomerism 24 12
13 ایزومری کوئوردیناسیون Coordination Isomerism [Co(NH 3 ) 6 ][Cr(CN) 6 ] hexaaminecobalt(iii) hexacyanochromate(iii) [Cr(NH 3 ) 6 ][Co(CN) 6 ] hexaaminechromium(iii) hexacyanocobaltate(iii) 25 ایزومری یونش Ionization Isomerism [CrSO 4 (NH 3 ) 5 ]Cl pentaaminsulfatochromium(iii) chloride [CrCl(NH 3 ) 5 ]SO 4 pentaaminchlorochromium(iii) sulfate 26 13
14 ایزومری آب پوشی Hydrated Isomerism 27 ایزومری اتصال Linkage Isomerism [Co(NH 3 ) 4 (NO 2 )Cl]Cl & [Co(NH 3 ) 4 (ONO)Cl]Cl [Co(SCN)(NH 3 ) 5 ] + & [Co(NCS)(NH 3 ) 5 ] + لیگاندهای دوسردندانه Ambidentate Ligands NCS - NO 2 - R-CONH
15 ایزومری اتصال Linkage Isomerism [Co(NH 3 ) 5 (NO 2 )]Cl 2 Pentaamminenitrocobalt(III) chloride [Co(NH 3 ) 5 (ONO)]Cl 2 Pentaamminenitritocobalt(III) chloride 29 20_441 ایزومری Isomerism Isomers (same formula but different properties) Structural isomers (different bonds) Stereoisomers (same bonds, different spatial arrangements) Coordination isomerism Linkage isomerism Geometric (cis-trans) isomerism Optical isomerism 30 15
16 Geometric Isomerism ایزومری هندسی cis-trans سیس ترانس
17 استریوایزومری Stereoisomerism 2- Optical 2- Stereoisomerism ایزومری نوری isomerism enantiomer 33 Optical Activity فعالیت نوری Optical isomers are isomers that differ in their ability to rotate the plane of polarized light 34 17
18 ایزومری نوری Optical Isomerism 35 Enantiomer Diasteriomer 36 18
19 پیوند در شیمی کوئوردیناسیون 1. Crystal Field Theory CFT 2. Molecular Orbital Theory MOT 37 کدام اوربیتال های فلر مرکزی در برهم کنش مستقیم با لیگاندها در میدان هشت وجهی است 38 19
20 شکافتگی اوربیتال های dدر میدان هشت وجهی میدان ضعیف میدان قوی 39 سری اسپکتروشیمیاییSeries The Spectrochemical I - < Br - < SCN - ~Cl - < F - < OH - ~ ONO - < C 2 O 4 2- < H 2 O< NCS - < EDTA 4- < NH 3 ~ pyr ~ en < phen < CN - ~ CO Mn 2+ < Ni 2+ < Co 2+ < Fe 2+ < V 2+ < Fe 3+ < Co 3+ < Mn 3+ < Mo 3+ < Rh 3+ < Ru 3+ < Pd 4+ < Ir 3+ < Pt
21 Strong field Weak field Strong field Weak field d 1 d 2 d 3 d 4 41 Strong field = Low spin (2 unpaired) d 4 Weak field = High spin (4 unpaired) PE < PE > 42 21
22 d 5 d 6 d 7 d 8 d 9 d
23 Relationship Between Absorbed and Observed Color 45 Effect of Ligands on Colors of Coordination Compounds 46 23
24 t 47 d-level Splitting 48 24
25 تاثیر لیگاند بر پتانسیل ردوکس 49 اربیتال مولکولی 50 25
26 خاصیت اسیدی و بازی در کمپلکس ها [Fe(H 2 O) 6 ] 3+ (aq) + H 2 O(aq) [Fe(H 2 O) 5 (OH)] 2+ (aq) + H 3 O + (aq) K a1 = 9*10-4 [Fe(H 2 O) 5 (OH)] 2+ (aq) + H 2 O(aq) [Fe(H 2 O) 4 (OH) 2 ] 2+ (aq) + H 3 O + (aq) K a2 = 5*
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