?????(coordination compound), ???

1
??? ????????????

• ?????(coordination compound), ???
• ???????(organometallic),???????M-C ?!
• ??????(cluster compound)???
• ?????????(non-stoichiometric compound),??????
• ?????(labelled compound)

2
9.1 ????????

• ????????????(??)
• ??????????,???????????,???????????
• ????????????,?????,??????????????
• ???????????,????,
• ????????????,?????,??????????,????????

3
1)??????????,???????????,???????????
MVS
4
?????(matrix isolation)
5
2)????????????,?????,??????????????

• P318

6
3)???????????,????

• ????

7
4)????????????,?????,??????????,????????
8
????????
9
supramolecular chemistry
??
The metal-directed assembly of a 2catenate and
subsequent demetallation yielding a 2catenand.
10
9.2 ??????????

• s?????
• p?????????????
• ?????????????????????????????????????
  (OMCOS)

???????????????????????-??????????????????,??????
?????,?????????????????,????????,?????????(???)???
???????????,??Comprehensive Organometallic
Chemistry??,??????
11
(No Transcript)
12
???Ziegler ?????????????TiCl4-AlEt3,???????TiCl3
1953 ????Natta ???????????(stereospecific)???????Z
iegler-Natta ???? ?Ziegler Natta ???
Serendipitous or serendipity
1951
13
?????????????????? (??????)M-C ?!(????? ????)
(Organometallic chemistry)

???????
?????
1827
Grignard RMgX
KPtCl3(C2H4)
1951
14
???

• (Fe(C5H5)2, ferrocene)
• ?????????????
• ???(Sandwich)
• ???????????,??
• ?????????

?????? Sandwich Structure
15
(No Transcript)
16
(No Transcript)
17
?????????
??????????????????n ??????,????????????(??)?????
?n??µ????????? ?? (C5H5)2Fe ?(?5- ?????)?(II)

???(µ-??)(?5-?????)?(0)
?3-????(II)?-µ-?????(III)
18
????????????

19
(No Transcript)
20
?. ???????????
??M???? ??? ?? M-L???
1 ?1 ??(H, X)
2 ?2 ??(CH2CH2)
2(4) ?2 ??(CH?CH)
2 ?1 ???(carbene)
21
3 ?1 ???(carbine)
3 , 1 ?3 , ?1 ?-???(allyl) C3H5
4 ?4 1,3-??? C4H6
4 ?4 ???? C4H4
5 ?5, ?3, ?1 ????? C5H5
6 ?6 ?
22
6 ?7 ??????? (C7H7)
6 ?6 ????(C7H8)
8, 6 ?8 , ?6 ????(C8H8)
4 ?4 ????(C8H8)
3 ?3 ????(C3H3)
4 ?4 ????(C7H8)
23
??????????????

• ?????(Octet rule)???????????????????8?????????PbE
  t4????(Cp2Be)
• ????????(effective atomic number
  rule)????????????????????????????????????????????
  ????,???????????????????18???????? ????

??18??????????????
24
????????(EAN??)
???18????,???????????????????????????????????(??d?
??1?s???p??)???? ????,???18??16?????18e?????
s?p?d???????,?????????,????????,
?????????M?L???????????,?18e?????????????????????
???,???????????????????,???16????????
??????????????,?????????
25
18????
??????? ???????d?s??????, ????d/s??,?????d???d???
?? ???d????
????????????????????????
26
(No Transcript)
27
L?M, ???, ????
M ? L, ??? , ??????
???d?????????????
28

• ?????????
• ????????????,????(CO)
• P342
  P339

29
The Nobel Prize in Chemistry 2005
Yves Chauvin
???????
Richard R. Schrock (left) and Robert H. Grubbs
30
???????
Metathesis a change-your-partners dance
31
???????
???????
Yves Chauvin ??
?????????????????????????????????,??????,
??????????,????????????????????????,????????????
??????????????????????????????
32
??????????
Richard R. Schrock
Robert H. Grubbs
33
?????
34
(No Transcript)
35
?? ???????, ??????????
??????? Cp???H? Li ??
36
??????
37
????????????????
???(Cluster)???
???????,???????????,?????????,M ? M ???????
M-M ???? Cr2O7 ??????,? Cr ? Cr
???O????????60?????????????,? K3W2Cl9,Fe2(CO)9????
????????,?????????????????
??????????M-M?,?????????,???????????????,?????????
??????????????????????
38
????M-M?????
???? Re3?d 4 ??,??dsp2??,4???????4?X-
?????dxy,dxz,dyz,dz2???????,2?Re???????--
Re2Cl82-???(????pm)
39
? Re?Re?????????????? ? ? ?? ? ??????
Re-Re?????,????????
Re2Cl82- ? Re ? Re ?d ??????
40
??(borane )
41
5 Wade??
1971????????K.Wade???????????????????????
??????????????????????????????Wade??(Wade.K.J.C.S
Chem, 1971, P292)? ??????????????????????
??, ???????????? ??b??????????,n??????,?
bn1 ???? (n???????)
?? BnHn2- ? BnHn2 bn2
?(?)??? (n1???????????)
?? BnHn4- ? BnHn4 bn3 ?????
(n2???????????) ??
BnHn6- ? BnHn6 bn4 ?????
(n3???????????) ?? BnHn8- ?
BnHn8
42
(No Transcript)
43
Lipscomb???????
Lipscomb???????????, ??????(topological
approach)????????, ?????
44
??
45
Applications of organoboranes in organic synthesis
H.C.Brown 1979 Nobel Prize
hydroboration
46
????????
47
???
48
??
49
??
50
9.4 ????????????

• ??????
• ????

51
9.5 ????????

• ??????
• ????
• ????????