2????????????(n-1)d?ns?nd??????????,????-?????????????:

1
(No Transcript)
2
(No Transcript)
3
(No Transcript)
4
??? ??????????????????
5
??????????????
1????????????? ?????????????, ????????????? ??????
??????? ????????????? ???????
6
2????????????(n-1)d?ns?nd??????????,????-?????????
???? 1)???????????,??????????? 2)?????????,?????
????? 3)??????????,????????? 4)?????????????????
?,???????????????
3??????????,???????? 1)???????????(????)?????????
?,??????NH3?H2O 2)???????????,?????????????,?????
?H????
7
3)??????????????????????,????????????????????????,
?????????????Cl-?Br-?I-?OH-
8
4)????????????????????????,???????????????????????
????,???/ ????????????????????,??????CO?????????
9
CO?????????????????????????????????(??)?????????
????????d???????????????CO??????????--Chatt?? X???
?,???C?O?C?C???? ???Raman????,C?O,C?C???????????
10
CO????????Blyholder??
CO???? HOMO 5?, localized on the carbon end of
the molecule, roughly nonbonding with respect to
the C-O bond. LUMO 2?, symmetrically
distributed along the molecular axis, antibonding
with respect to C-O
11

• When CO chemisorbs on metal surfaces,
• 5? orbital interacts strongly with the metallic
  electronic states, and the electron density of
  the 5? orbital is donated to the metal and new
  hybrid electronic states are formed (donation),
  these are predominately localized about the
  carbon end of the molecule
• The 2? accepts electron density from the metal
  from a process known as back donation, new hybrid
  electronic states are constructed which are
  primarily localized about the CO molecule.

The overlap of the 5? orbital with the metal
states is most favorable if the molecule is
oriented with the carbon end toward the surface
and the overlap of 2? orbital with the metal
states is most favored by a linear geometry. Thus
it can be predicted that the CO molecule should
chemisorb carbon end down with its axis along the
normal to the surface. This expectation is
confirmed by experiments.
12
The 5? orbital is nonbonding in CO. Therefore,
modification of this orbital does not have a
strong influence on the intramolecular C-O bond
the 2? orbital is antibonding with respect to
the C-O bond, thece, the increased occupation of
the 2? engendered by back donation leads to a
weakening of the C-O bond. Thats the reason for
the observed change of the C-O stretch vibration
frequency of CO upon chemisorption on metal
surfaces Gas phase gt on-top gt twofold bridge gt
fourfold hollow (fcc(100) surface).
The above Blyholder model, the use of frontier
orbitals and analogies to coordination chemistry
have been successful in explaining the
qualitative trends observed in the chemisorption
of small molecules. But to understand
quantitatively the bonding in an
adsorbate/substrate system, it may be necessary
to consider other orbitals beyond the frontier
orbitals.
13
TDS
RAIRS
14
200K
100K
Model
RAIRS
15
4?????????,?????????????????????????????,?????????
?(dx2-y2?dxy)???/ ??????????????????,?????dx2-y2??
????????????,?????dxy?????
5???????????????????-???????????,????????????,????
????????????????????,?????????????????????????????
???Fermi???
16
????????????????????????, ????????????????????????
??????????,????????,????????? ?????????,??????????
?,???????????,???????????CO??????,???????????????
???????????,??????????????????????????,???????????
?????????????????????????,?????
17
(No Transcript)
18
(No Transcript)
19
?????????????????
1????????
?????????????,?????A?B????????????? ?????????
???A?B??????,??????????????
2?????/????
?????????????????,?????????2 ??????,?Rh?H2?HI?CH3I
????????????
20
3?????????????????????????-??????????,????M???L??
???????,???1,1????????????????,???1,2???
????1,2??
?CO?1,1??
?????-????????????
21
??????
???????? RuCl63- Co(CN)53-
RhCl(PPh3)3(Wilkinson???)
22
(No Transcript)
23

• Keys to the success of the rhodium phosphine
  complexes in olefin
• hydrogenation catalyst are the following
• Rh exists in two oxidation states separated by
  two unites, allowing the oxidative addition and
  reductive elimination to occur readily
• There are no intermediates that are so stable as
  to form bottlenecks in the cycle. The
  intermediates are in delicate balance. They are
  all present in low concentrations, and they react
  predominantly within the cycle rather than to
  give dead-end complexes. When the phosphine
  concentration is too high or the hydrogen
  concentration is too low, most of the rhodium is
  present as RhCl(PPh3)3 and the dimeric complex
• When olefins that are too tightly bound to
  the rhodium are used, the catalysis is also
  showed down. These compounds are competitive
  inhibitors. Competing ligands such as pyridine
  are bonded to the rhodium so tightly that they
  shut down the cycle these ligands are called
  poisons.

24
Relative activities of rhodium complexes as
catalyst precursors in the Wilkinson
hydrogenation of cyclohexene Rh complex
relative
activity RhClP(p-C6H4Cl)33
1.7 RhClP(p-C6H5)33

41 RhClP(p-C6H4-CH3)33
86 RhClP(p-C6H4-OCH3)33
100
25
?????? ????
26
?????????-Wacker??
????????? 1)???Pd(II)?????,Pd(II)???Pd(0)
2)Pd(0)????Pd(II),Cu2???Cu 3)Cu?????????C
u2
27
????
?
?
28
??????
?
?
??????
29
?????????
???? 1)Pd(II)???Cl-?????PdCl42-?????,??????Cl-?
??????? 2)CuCl2????,1??PdCl2????1??C2H4,?????????
?????????????????????PdCl2?????,?????CuCl??,??????
3)??????,????????Pd(II)?????,?Cl-?????,?H?????
30
4)????????????,???????????????????????????,???????
?????????????? 5)??????????,??????????D,????????H
???????? 6)???????,????????,?????????????????????
? ????????????? 7)??????,???????????????Pd2???
?,?CD2CD2??CH2CH2?,?????????,????????? 8)??????
???,?????????,??????
31
???????
1??-???????
???Co2(CO)3 RhCl(CO)(PPh3)3???,???
???/????
????? ???? 1)???Rh?????Rh-H?????????? 2)CO?
?Rh-C? 3)??????????????
32
(No Transcript)
33
???????????,???????????
??????????,??????2-??-1-??
34
?????????????????????PPh3/RhHCO(PPh3)3????
The activity of the catalyst depends on the
concentration of the ligands. A general
conclusion can be inferred from this observation
any groups that can bond to the catalyst in
competition with the reactants can be a reaction
inhibitor, but the role of phosphine is more
complicated than that of a simple inhibitor.
35
2?????????
IR??????(CH3CO)Rh(CO)I3-??? CO?????????? ?????
?Rh????????,?CO???,?????????????In-situ-IR????Rh(
CO)2I2?
36
??Ziegler-Natta??-?-???????
?????????-TiCl3?????????Al(C2H5)2Cl
???????????2?105kPa?????????????????????????? ??
???????Ziegler?????????????????????????? ??????
????????-???Ziegler?????????????R?S???????????????
?????????? ??????????????-??????????R?S???????
??????????????-????????R?S?????????
37
?????
?????
?????
38
Cosse-Arlman?????? 1)???????????Ti-C2H5?Cl-?????
?? 2)??????????Chatt?????Cl-????Ti-??????
39
3)???? ??????????????,???????,???????????????
???????,???14C2H5?TiCl3?????,????????????????14C2
H5?? 4)?????
40
???Ti3????
??????????
?????????-TiCl3?-TiCl3????????,??????????? TiCl3?
??Cl-????,Ti?????????
41
?-TiCl3????????Cl-???,Ti3???-?(2/3)-?-?(2/3)???
????????????
42
II?(R???)?I?(Cl-??)?? ?????I???,??????????II?,???
I?????????,??????,??????????
43
????????,???I????,??CH2??,???CH??,??????CH3?????1?
Cl-?????-TiCl3????,?????????????????,???????CH3???
???????????
44
?-TiCl3???Ti3????,?????????????Cl-?????????????T
iCl3?????????????????Ti2?Cl-??????????????,??????
??????????,??????????,????-TiCl3????????,????????
,???????????????