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第二十五章 无机化学新兴领域简介 PowerPoint PPT Presentation


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第二十五章 无机化学新兴领域简介. §25 —1 有机金属化学 §25 —2 金属原子簇化学 §25 —3 非金属原子簇化学 §25 —4 生物无机化学简介 §25 —5 无机固体化学. 有机金属化学是有机化学和无机化学交 叠的一门分支课程,主要讲述含金属离子的 有机化合物的化学反应、合成等各种问题。 其中的化学反应,包含了许多催化性质的反 应以及跟金属配位有关的化学反应,甚至有 些是运用在于医药上,如用于治疗糖尿病的 含钒的配合物。. 25-1-1 有机金属化合物的分类. 25-1-2 过渡金属羰基化合物

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第二十五章 无机化学新兴领域简介

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25 1

25 2

25 3

25 4

25 5


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25-1-1


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25-1-2

CO

CONi(CO)4NiC147 kJmol1II(150 kJmol1)CO(142 kJmol1)

, (O)dMO, ML

EAN


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Ni(CO)4,1890MondCO(CO)NiCO

Ni4CO Ni(CO)4(m.p.25) Ni4CO

FeCoNiCoNiCO(CoFeCONi)NiCoNi


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1891, MondCO493 K2107 PaFeFe(CO)5

Fe 5CO Fe(CO)5

Ni Fe

493K, 20MPa


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420K30MPa

A1C13

420K25MPa

(1)CO

Ni4CO Ni(CO)4(m.p.25) Ni4CO

(2)

NaAlMgCOCOH2

2CoCO36CO4H2 Co2(CO)8 4H2O

CrC136COA1 Cr(CO)6A1C13

OsO49CO Os(CO)54CO2


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(3) , :

3 Os(CO)5 Os3(CO)123CO

2 Fe(CO)5 Fe2(CO)9CO

Co2(CO)6 Co4(CO)12

(4)

3Fe(CO)5Ru2(CO)12 FeRu2(CO)12

Fe2Ru(CO)12CO

UV,

320K

380K


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2.

(1)

Fe(CO)53NaOH Na[HFe(CO)4]Na2CO3

H2O

(2)

Na[Co(CO)4]H H[Co(CO)4]Na

(3)X2NO

Fe2(CO)94NO 2Fe(CO)2(NO)2 6CO

(4)

Mn2(CO)10Br2 2Mn(CO)5Br


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3.

N2NO+CNCOCO

N2

N2CO3gd N21g


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CON2 CO N2 CO; N2CO, N2d CON2N2


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N2 d


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N2NNN2N2(()/2)N2100300cm1600cm1N2N2N2NH3N2


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N2

N2


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CON2NO CNAR3


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4. (EAN)

EAN d 18,

EAN18(d1sp)


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181618espd, ML18e16 EAN18e16e


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18e:

COHRAr

Fe(CO)4H2 Ni(CO)4

Fe2+ 6 Ni 10

4CO 428 )4CO 428

)2H 224 10818

68418


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Mn(CO)6: Mn+ 716 6CO 6212

61218

Co(CO)4 Co 9110 4CO 428

10818

MMMCOM Fe2(CO)9 FeFe 3

MCOM

Fe8CO6, CO 3 Fe 1,

863118


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NO:

NO

Mn(CO)4(NO) Mn(CO)4(NO)

NO2 NO314

4CO 8 4CO 8

) Mn718 ) Mn+ 71 6

28818 48618


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n 1C5H5()

5C5H5 3CH2CH2CH36C6H6()

n n hapto, n1 1Fe(CO)2(5C5H5)(1C5H5)

2CO4 5C5H55(6), 1C5H51(2)Fe8(6),

4518(4626)18

Mn(CO)4(3CH2CH2CH3)

4CO8 (3CH2CH2CH3)3(4), Mn7(6),

837 (846)18

Cr(6C6H6)2

2(6C6H6)12Cr 6,12618


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5. EAN

1816

a [M(CO)n]

b HM(CO)n M(CO)nX

c


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Cr(CO)6 C6H6

6CO

[Cr(C6H6)(CO)3]3CO

Mn2(CO)10 Na

Mn2(CO)10 721023417Na [Mn(CO)5] Na


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CO CO CO

CO Ir CO

CO Ir Ir CO

CO Ir CO

CO CO CO

MM

Ir4(CO)12 4Ir4936 12CO12224

60 Ir 15e

EANIrIrMM 18e ,


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EANV(CO)617, V2(CO)12 V(CO)6 V2(CO)12 V7VV V(CO)6


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25-1-3

  • 1.

  • ()


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[PtC12(NH3)(C2H4)] ()()

[Ni(C5H5)2] ()()

[Ni(NO)3(C6H6)] ()(0)

Cr(CO)3(C6H6)] ()(0)

[ReH(C5H5)2] ()()

(1,5)(0)


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2. (Zeise salt)

(K[Pt(C2H4)C13])(2)()18251954

Csp2 C p

*


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[Pt(C2H4)C13]Pt() d 8 dsp2Cl(Cl) , (,Pt())Pt() d * ( Pt())


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C4H6() Fe(CO)5

2 CO


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3.

** d


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4.

Sandwich compound

()


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1951 ( ) FeCl3 :

(C5H5)2FeFe3+Fe2+Fe2+:

2 FeCl2 (C5H5)2FeMgBr2MgCl2


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Ni2Cp3+


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3CrC132A1A1Cl36C6H6 [(C6H6)2Cr][A1C14]

0

2[(C6H6)2Cr]S2O424OH (C6H6)2Cr2SO322H2O


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m.p.284285

2(C6H6)2CrO22H2O 2[(C6H6)2Cr]OHH2O2

Cr18 9


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25 2

33

HenNenArn

KrnXenClusters Cotton F. A.

1966 clusters

cluster compound


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2070

LipscombSidgwick

(EAN)Wade

Cotton-


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1.

MM

Mn2(CO)10

d2sp3

Mn

Mn


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Co2(CO)8

COCoCo6 d2sp3 CoCo


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CO

CoCo6

d2sp3

CoCo


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  • CONO

    ClORSP4As4S8Sn4C60


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