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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



25-1-1


25-1-2

CO

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

, (O)dMO, ML

EAN


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

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

FeCoNiCoNiCO(CoFeCONi)NiCoNi


1891, MondCO493 K2107 PaFeFe(CO)5

Fe 5CO Fe(CO)5

Ni Fe

493K, 20MPa


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


(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


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


3.

N2NO+CNCOCO

N2

N2CO3gd N21g


CON2 CO N2 CO; N2CO, N2d CON2N2


N2 d


N2NNN2N2(()/2)N2100300cm1600cm1N2N2N2NH3N2


N2

N2


CON2NO CNAR3


4. (EAN)

EAN d 18,

EAN18(d1sp)


181618espd, ML18e16 EAN18e16e


18e:

COHRAr

Fe(CO)4H2 Ni(CO)4

Fe2+ 6 Ni 10

4CO 428 )4CO 428

)2H 224 10818

68418


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


NO:

NO

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

NO2 NO314

4CO 8 4CO 8

) Mn718 ) Mn+ 71 6

28818 48618


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


5. EAN

1816

a [M(CO)n]

b HM(CO)n M(CO)nX

c


Cr(CO)6 C6H6

6CO

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

Mn2(CO)10 Na

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


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 ,


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


25-1-3

  • 1.

  • ()


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

[Ni(C5H5)2] ()()

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

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

[ReH(C5H5)2] ()()

(1,5)(0)


2. (Zeise salt)

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

Csp2 C p

*


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


C4H6() Fe(CO)5

2 CO


3.

** d


4.

Sandwich compound

()


1951 ( ) FeCl3 :

(C5H5)2FeFe3+Fe2+Fe2+:

2 FeCl2 (C5H5)2FeMgBr2MgCl2




Ni2Cp3+



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

0

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


m.p.284285

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

Cr18 9


25 2

33

HenNenArn

KrnXenClusters Cotton F. A.

1966 clusters

cluster compound


2070

LipscombSidgwick

(EAN)Wade

Cotton-



1.

MM

Mn2(CO)10

d2sp3

Mn

Mn


Co2(CO)8

COCoCo6 d2sp3 CoCo


CO

CoCo6

d2sp3

CoCo


  • CONO

    ClORSP4As4S8Sn4C60


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