26chem.yazd.ac.ir/gorji/Lecture/General Chemistry 2/General Chemistry... · Cr chromium chromate Mn...

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Coordination Chemistry

شیمی کوئوردیناسیون

Mortimer, C.E.; Müller, U. “Chemie“ 10th Ed. Stuttgart 2010.

Alireza Gorjiagorji@yazd.ac.ir

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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N

NH NH

N

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Myoglobin

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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 19agorji@yazd.ac.ir 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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d9

d5 d6 d7

d8 d10

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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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