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Coordination Chemistry
شیمی کوئوردیناسیون
Mortimer, C.E.; Müller, U. “Chemie“ 10th Ed. Stuttgart 2010.
Alireza [email protected]
Department of Chemistry, Yazd University
Coordination Chemistry
Alfred Werner1866-1919
Nobel prize 1913
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Transition Metals فلزات واسطه20_432
Sc
Y
La*
Ac†
Ti
Zr
Hf
Unq
V
Nb
Ta
Unp
Cr
Mo
W
Unh
Mn
Tc
Re
Fe
Ru
Os
Co
Rh
Ir
Ni
Pd
Pt
Cu
Ag
Au
Zn
Cd
Hg
Ce
Th
Pr
Pa
Nd
U
Pm
Np
Sm
Pu
Eu
Am
Gd
Cm
Tb
Bk
Dy
Cf
Ho
Es
Er
Fm
Tm
Md
Yb
No
Lu
Lr
d-block transition elements
*Lanthanides
†Actinides
f-block t ransition elemen ts
Uns Uno Une Uun Uuu
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Lewis base B Ligand (nutral molecule or ion)
Lewis acid A Metal atom or Metal ion
Coordination compounds Complexes
A + :B A-B
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complex
central atom
ligands
coordination number
Terminology for Complexes
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کمپلکسهای چهاروجهی
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کمپلکسهای مسطح مربع
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Coordination Number: 5
Coordination Number: 6
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Coordination Environment of Fe2+ in Oxymyoglobin and Oxyhemoglobin
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نامگذاری
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• Ligands• Monodentate
• Multidentate
• Bidentate
• Tridentate
• Tetradentate
نامگذاری
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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 [email protected] Yazd University
[Ag(NH3)2]Cl diamminesilver(I) chloride
K3[Fe(CN)6] potassium hexacyanoferrate(III)
[Cu(NH3)4]SO4 tetraamminecopper(II) sulfate
[Co(NH3)6]Cl3 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)2Cl2]F dichlorobis(ethylenediamine)cobalt(III) fluoride
[Fe(bipy)3]Cl2 tris(bipyridine)iron(II) chloride
Nomenclature of Coordination Complexes
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[Co(NH3)4Cl2]+ tetraamminedichlorocobalt(III) ion
[Pt(NH3)BrCl(CH3NH2)] amminebromochloromet hylamineplatinum(II)
[Pt(NH3)4]2+ tetraammineplatinum(II) ion
[PtCl4]2- tetrachloroplatinate(II) ion
[PtCl6]2- hexachloroplatinate(IV) ion
Isomer designations come before the rest of the name and in italics
cis-diamminedichloroplatinum(II)
trans-diamminedichloroplatinum(II)
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K2[Co(NH3)2Cl4]
potassium diamminetetrachlorocobaltate(II)
[Co(NH3)4Cl2]Cl
tetraamminedichlorocobalt(III) chloride
[Co(NH3)4Cl2]+
tetraamminedichlorocobalt(III) ion
[Ti(H2O)6][CoCl6]
hexaaquatitanium(III)hexachlorocobaltate(III)
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K3[Fe(CN)6]
potassium hexacyanoferrate(III)
[Fe(CN)6]3-
hexacyanoferrate(III) ion
[Co(NH3)6]3+
[Fe(SCN)6]3-
[Co(en)3]3+
[Cr(C2O4)3]3-
[Fe(EDTA)]-1
[Co(EDTA)]-1
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Isomers
(same formula but different properties)
Stereoisomers
(same bonds, different
spatial arrangements)
Structural
isomers
(different bonds)
Optical
isomerism
Geometric
(cis-trans)
isomerism
Linkage
isomerism
Coordination
isomerism
Isomerism ایزومری
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Coordination Isomerism ایزومری کوئوردیناسیون
[Co(NH3)6][Cr(CN)6]
hexaaminecobalt(III) hexacyanochromate(III)
[Cr(NH3)6][Co(CN)6]
hexaaminechromium(III) hexacyanocobaltate(III)
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Ionization Isomerism یونش ایزومری
[CrSO4(NH3)5]Cl
[CrCl(NH3)5]SO4
pentaaminsulfatochromium(III) chloride
pentaaminchlorochromium(III) sulfate
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Hydrated Isomerism ایزومری آب پوشی
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[Co(NH3)4(NO2)Cl]Cl & [Co(NH3)4(ONO)Cl]Cl
[Co(SCN)(NH3)5]+ & [Co(NCS)(NH3)5]
+
Ambidentate Ligands لیگاندهای دوسردندانه
NCS- NO2- R-CONH2
Linkage Isomerism ایزومری اتصال
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[Co(NH3)5(NO2)]Cl2Pentaamminenitrocobalt(III) chloride
[Co(NH3)5(ONO)]Cl2Pentaamminenitritocobalt(III) chloride
Linkage Isomerism ایزومری اتصال
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Isomers
(same formula but different properties)
Stereoisomers
(same bonds, different
spatial arrangements)
Structural
isomers
(different bonds)
Optical
isomerism
Geometric
(cis-trans)
isomerism
Linkage
isomerism
Coordination
isomerism
Isomerism ایزومری
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Geometric Isomerism ایزومری هندسیcis-trans ترانس –سیس
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enantiomer
2- StereoisomerismStereoisomerism استریوایزومری
2- Optical isomerism ایزومری نوری
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Optical Activity فعالیت نوری
Optical isomers are isomers that differ in their
ability to rotate the plane of polarized light
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Optical Isomerism ایزومری نوری
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EnantiomerDiasteriomer
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1. Crystal Field Theory CFT
2. Molecular Orbital Theory MOT
در شیمی کوئوردیناسیونپیوند
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کدام اوربیتال های فلر مرکزی در برهم کنش مستقیم با لیگاندها در میدان هشت وجهی است؟
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میدان قوی میدان ضعیف
در میدان هشت وجهیdاوربیتال های شکافتگی
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• I- < Br- < SCN- ~Cl- < F- < OH- ~ ONO- <
C2O42- < H2O< NCS- < EDTA4- < NH3 ~ pyr
~ en < phen < CN- ~ CO
• Mn2+ < Ni2+ < Co2+ < Fe2+ < V 2+ < Fe3+ <
Co3+ < Mn3+ < Mo3+ < Rh3+ < Ru3+ < Pd4+ <
Ir3+ < Pt4+
The Spectrochemical Series اسپکتروشیمیاییسری
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d1 d2
d3 d4
Strong field Weak field Strong field Weak field
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d4
Strong field =
Low spin
(2 unpaired)
Weak field =
High spin
(4 unpaired)
PE < PE >
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Relationship Between Absorbed and Observed Color
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Effect of Ligands on Colors of Coordination Compounds
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t
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d-Level Splitting
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تاثیر لیگاند بر پتانسیل ردوکس
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اربیتال مولکولی
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خاصیت اسیدی و بازی در کمپلکسها
[Fe(H2O)6]3+(aq) + H2O(aq) [Fe(H2O)5(OH)]2+(aq) + H3O+(aq)
Ka1 = 9*10-4
[Fe(H2O)5(OH)]2+ (aq) + H2O(aq) [Fe(H2O)4(OH)2]2+(aq) + H3O+(aq)
Ka2 = 5*10-4
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