第 9章 金属原子簇和金属金属多重键存在 M－ M键的化合物称为簇合物（ cluster) (M为 3以上）
羰基原子簇,Rh6(CO)16,Co4(CO)12（ 0价）（ 低价 ）
卤化物类原子簇,Mo6Cl84+ （ +2价） （ 高价 ）
一 金属原子簇
1,Carbonyl Cluster
低核羰基原子簇 (Low Nuclear Carbonyl Cluster ),
18电子规则
Fe3(CO)10(?–CO)2 M3(CO)12
M4(CO)9(?-CO)3 Ir4(CO)12
M6(CO)12(?3–CO)4
不符合 18电子规则（ 18 )1
3
Medium size Carbonyl Cluster
Wade规则,For Medium size Carbonyl Cluster
M(CO)3与 BH（或 CH）的等瓣关系，
PSEPT (多面体 骨架电子数理论 ),(v+ x-12)
(2n+2),(2n+4),(2n+6)骨架电子数规则
TEC(总电子数 )方法
(9N-L)规则
(nxc?)规则
Wade规则,M(CO)3与 BH（或 CH）的等瓣关系，
PSEPT （ Polyhedral Skeletal Electron Pair
Theory)多面体 骨架电子数理论分子片 的 骨架电子数 (v+ x-12)
v为中心金属的价电子数,x为配体提供的总电子数
(2n+2),(2n+4),(2n+6) 骨架电子数规则
or (n+1),(n+2),(n+3) 骨架 电子对数 规则闭式,开式,网式
BH
一个 Co(CO)2分子片的 骨架电子数：
v=9
x=2?2=4
(v+x-12)=1
6个 Co(CO)2分子片
1?6=6
4个 CO=8
总骨架电子数 =6+8=14
总骨架电子对数 =7=6+1
n+1 闭式结构或者：
TEC=6?9+16?2=86
总骨架电子数 =86-12?6=14
骨架电子对数 =7
C
Fe5(CO)15C
一个 Fe(CO)3分子片的 骨架电子数：
v=8
x=3?2=6
(v+x-12)=2
5个 Fe(CO)3分子片
2?5=10
1个 =4
总骨架电子数 =10+4=14
总骨架电子对数 =7=5+2
n+2 开式结构或者：
TEC=5?8 +2?15 + 4
=74
总骨架电子数 =74-12?5
=14
骨架电子对数 =7
J,Am,Chem,Soc,1996,118,7869-7870
An Unprecedented High-Nuclearity Closest-Packed
Bimetallic Palladium Carbonyl Cluster:
[Pd33Ni9(CO)41(PPh3)6]4- Containing a Pseudo-D3h
hcp Pd33Ni9 Core
High-Nuclear Carbonyl Cluster:
若按照 Wade 规则计算骨架电子数 =14
不符合 Wade规则
The 41 CO consist of 5 terminal and 36 bridging
ligands,The terminal COs are coordinated to the
three corner Ni atoms in the middle layer and to the
two central Pd atoms in the top and bottom layers,
Of the 36 bridging COs,24 are edgebridging and the
other 12 are face-bridging.
P d
P d
P d
P d
P d
P d
N i
N i N i
P d
P d
P d P d
P d
P dP d
Pd6 Pd
7Ni3
Mo6Cl84+ Mo6S84 –
Mo(II) 簇电子数,4× 6 = 24e
Mo—Mo间的电子数,24/12(棱 )=2
Mo—Mo 单键 (2e) ~ 2.60?
2,高价过渡金属卤化物 (硫化物 )原子簇
M6X8 或 [ M6(?3-X)8 ]
Chevrel phase,PbM6S8
高价过渡金属卤化物原子簇 M6X12
Nb6Cl122+
Nb(氧化态 =14/6) 簇电子数,（ 5 –14/6)× 6 =16e
（或者 簇电子数 =5× 6 –12-2=16）
Nb—Nb间的电子数,16/12(棱 )=4/3e
Nb—Nb 键级,2/3 ~ 2.90?
Synthesis and Structural
Characterization of
Compounds Containing the
[Zr6Cl18H5]3-
Cluster Anion,Determination
of the Number of Cluster
Hydrogen Atoms
Linfeng Chen,F,Albert
Cotton,* and William A,
Wojtczak
Inorg,Chem,1997,36,4047-
4054注意结构的对称性！
3,过渡金属 -硫,原子簇”
[Fe4S4(SPh)4]2-结构
F e
S
S
F e
F e
S
F e
S
Fe4S4基本单元生物体内的电子转移反应
Fe4S43++e-? Fe4S42+ +e-? Fe4S4+
Fe33+,Fe2+ /Fe23+,Fe22+ / Fe3+,Fe32+
Fe4S*4Cys4 n-
Schematic structures
(A) a proposed 6-Fe cluster
in [Fe]-hydrogenase,
(B) the binuclear site in D,
gigas hydrogenase,
(C) the P cluster of
nitrogenase (Rees),
(D) the P cluster of
nitrogenase (Bolin),
(E) the cofactor cluster of
nitrogenase,
(F) [MFe4S6(PEt3)4Cl] (M=
V,Mo).
二,金属 -金属多重键 (multi-bonds)
1935年,C,Brosset
K3W2Cl9 中,W—W 240pm (2.40?)
W单质中,W—W 275pm
1975年 F,A,Cotton,
Re2Cl82– (d4) Re—Re 224pm
W W
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
F,A,Cotton,
―Highlights From Recent Work On Metal -Metal Bonds‖
Inorg,Chem,39(1998)5710-5720
d3
C rCrC C
N N
B o n d B o n dR a t i o R a t i o
0,7 8 3
0,7 8 6
0,7 6 7
0,8 0 7
0,8 4 8
Mo Mo
Re Re
多重键缩短比 (多重键键长 /单键键长 )
Re Re
C lC l C l
C l
C l
C l
C l
C l
Re2Cl82– Cr2Ac4.2H2O
四方棱柱构形
C r C r O H 2H 2 O
O
C
O
C H 3
5个 d轨道的形成的 1?个 2?个 2个?键
dx2-y2轨道和 dxy的形成 2个?键四方棱柱 M-M间的 d 轨道能级图
*
*
*
M2L8四方棱柱 的 d轨道能级图
[Re2Cl8]2-+ PR3?
2?4?2 (4级键）
1,2,7-Re2Cl5(PMe3)3
2?4?2?*1 (3.5级键）
1,3,6,8-
Re2Cl4(PMe3)4+Cl2?
2?4?2?*2 (3级键）
1,3,6-Re2Cl5(PMe3)3
2?4?2?*1 (3.5级键）
[Re2Cl8]2- + PMe3 (惰性气氛，苯溶剂）?1,2,5,7-Re2Cl6(PMe3)4
(+3) (+3)
2?4?2 (4级键）
Re—Re 3.8486? 不存在金属 -金属键
(+3) (+4)
[Re2Cl8]2-+ PEt2H ( HCl，苯 ）? 1,2,5,6-Re2Cl4(?-PEt2)(PEt2H)4
Trinuclear complexes
di-2-pyridylamine (dpa-)
[Cr3(dpa)4Cl2]+
从高度对称到非对称一维导体（分子导线）
由 Pt的 5dz2轨道重叠形成导带
Pt(CN)4n-的链状分子讨论,K2Pt(CN)4的电导很小,Pt被部分氧化后电导增大，原因？
四氰基铂酸钾 K2Pt(CN)4X0.3 （ KCP）
配合物 Pt的价态
Pt?Pt间距 /pm
颜色 导电性
/1.cm?1
金属 Pt
K2Pt(CN)4?3H2O
K2Pt(CN)4Br0.3?3H2O
K2Pt(CN)4Cl0.3?3H2O
K1.75Pt(CN)4?1.5H2O
Cs2Pt(CN)4(FHF)0.39
0
+2.0
+2.3
+2.3
+2.25
+2.39
277.5
348
288
287
296
283
金属白色青铜色青铜色青铜色金色
~9.4?101
5?10?7
4-830
~200
~70-100
未知阴离子堆垛结构的四氰基铂酸盐
Cu—Cu ~ 2.44-2.81?
r(Cu2+) ~ 0.6-0.8?
Cu—Cu间 无化学键,
磁性具有强温度相关性
eff = ~ 1.4BM/Cu atom
A.F,Cotton
Adv,Inorg,Chem,(1999).
p.870
Cu2(CH3COO)4.2H2O，是否存在 Cu—Cu间的?键？
Binuclear complexes,I,Electronic structure of copper acetate,
Forster,Leslie S.; Ballhausen,C,J,Univ,Copenhagen,Acta
Chemica Scandinavica (1962),16 1385-92,CODEN,
ACHSE7 ISSN,0904-213X,Journal written in English,
CAN 57:73457 AN 1962:473457 CAPLUS
Abstract
Electronic structure of the dimeric Cu acetate Cu2(Ac)4.2H2O
was considered by using a tentative mol,orbital scheme,A
rather strong s bond exists between the 2 Cu units,in contrast
to a former proposal of a d bond (Figgis and Martin,CA 51,
1672h),Although the proposed model gives a satisfactory qual,
account of the exptl,data (antiferromagnetism,absorption
spectrum,and g factors),alternative models may also be
consistent with the rather limited data,
Dinuclear copper(II) acetate monohydrate,Redetermination of the
structure by neutron-diffraction analysis,Brown,George M.;
Chidambaram,R,Chem,Div.,Oak Ridge Natl,Lab.,Oak Ridge,
TN,USA,Acta Crystallographica,Section B,Structural
Crystallography and Crystal Chemistry (1973),29(Pt,11),2393-
403,
Abstract
The crystal structure of dinuclear Cu(II) acetate monohydrate,
Cu2(O2CCH3)4.2H2O (van Niekerk and Schoening,1953),was
refined by the full-matrix least-squares method using 3-dimensional
neutron data and revised cell parameters [a 13.167 (4),b 8.563 (2),c
13.862 (7),ANG.,b 117.019 (2)° (lCu Ka1 = 1.54051,ANG.),space
group C2/c,and Z = 4],A reasonable description of the Me groups,
which are in large-amplitude torsional oscillation,was obtained by
using a special model,R(F) = 0.061 and R(F2) = 0.072 for F2 >?,
excluding the very weak reflections and reflections mildly affected
by extinction,The intramolecular Cu-Cu vector is 2.6143 (17),ANG,
long and oriented almost exactly as reported from measurements of
magnetic anisotropy and electron spin resonance
Rhodium acetate dimer Rh2(OAc)4(H2O)2
Cu2(OAc)4L2 where L = pyridine or 0.5 pyrazine
Rh2(OAc)4(H2O)2中 Rh- Rh的键级是多少？
羰基原子簇,Rh6(CO)16,Co4(CO)12（ 0价）（ 低价 ）
卤化物类原子簇,Mo6Cl84+ （ +2价） （ 高价 ）
一 金属原子簇
1,Carbonyl Cluster
低核羰基原子簇 (Low Nuclear Carbonyl Cluster ),
18电子规则
Fe3(CO)10(?–CO)2 M3(CO)12
M4(CO)9(?-CO)3 Ir4(CO)12
M6(CO)12(?3–CO)4
不符合 18电子规则（ 18 )1
3
Medium size Carbonyl Cluster
Wade规则,For Medium size Carbonyl Cluster
M(CO)3与 BH（或 CH）的等瓣关系，
PSEPT (多面体 骨架电子数理论 ),(v+ x-12)
(2n+2),(2n+4),(2n+6)骨架电子数规则
TEC(总电子数 )方法
(9N-L)规则
(nxc?)规则
Wade规则,M(CO)3与 BH（或 CH）的等瓣关系，
PSEPT （ Polyhedral Skeletal Electron Pair
Theory)多面体 骨架电子数理论分子片 的 骨架电子数 (v+ x-12)
v为中心金属的价电子数,x为配体提供的总电子数
(2n+2),(2n+4),(2n+6) 骨架电子数规则
or (n+1),(n+2),(n+3) 骨架 电子对数 规则闭式,开式,网式
BH
一个 Co(CO)2分子片的 骨架电子数：
v=9
x=2?2=4
(v+x-12)=1
6个 Co(CO)2分子片
1?6=6
4个 CO=8
总骨架电子数 =6+8=14
总骨架电子对数 =7=6+1
n+1 闭式结构或者：
TEC=6?9+16?2=86
总骨架电子数 =86-12?6=14
骨架电子对数 =7
C
Fe5(CO)15C
一个 Fe(CO)3分子片的 骨架电子数：
v=8
x=3?2=6
(v+x-12)=2
5个 Fe(CO)3分子片
2?5=10
1个 =4
总骨架电子数 =10+4=14
总骨架电子对数 =7=5+2
n+2 开式结构或者：
TEC=5?8 +2?15 + 4
=74
总骨架电子数 =74-12?5
=14
骨架电子对数 =7
J,Am,Chem,Soc,1996,118,7869-7870
An Unprecedented High-Nuclearity Closest-Packed
Bimetallic Palladium Carbonyl Cluster:
[Pd33Ni9(CO)41(PPh3)6]4- Containing a Pseudo-D3h
hcp Pd33Ni9 Core
High-Nuclear Carbonyl Cluster:
若按照 Wade 规则计算骨架电子数 =14
不符合 Wade规则
The 41 CO consist of 5 terminal and 36 bridging
ligands,The terminal COs are coordinated to the
three corner Ni atoms in the middle layer and to the
two central Pd atoms in the top and bottom layers,
Of the 36 bridging COs,24 are edgebridging and the
other 12 are face-bridging.
P d
P d
P d
P d
P d
P d
N i
N i N i
P d
P d
P d P d
P d
P dP d
Pd6 Pd
7Ni3
Mo6Cl84+ Mo6S84 –
Mo(II) 簇电子数,4× 6 = 24e
Mo—Mo间的电子数,24/12(棱 )=2
Mo—Mo 单键 (2e) ~ 2.60?
2,高价过渡金属卤化物 (硫化物 )原子簇
M6X8 或 [ M6(?3-X)8 ]
Chevrel phase,PbM6S8
高价过渡金属卤化物原子簇 M6X12
Nb6Cl122+
Nb(氧化态 =14/6) 簇电子数,（ 5 –14/6)× 6 =16e
（或者 簇电子数 =5× 6 –12-2=16）
Nb—Nb间的电子数,16/12(棱 )=4/3e
Nb—Nb 键级,2/3 ~ 2.90?
Synthesis and Structural
Characterization of
Compounds Containing the
[Zr6Cl18H5]3-
Cluster Anion,Determination
of the Number of Cluster
Hydrogen Atoms
Linfeng Chen,F,Albert
Cotton,* and William A,
Wojtczak
Inorg,Chem,1997,36,4047-
4054注意结构的对称性！
3,过渡金属 -硫,原子簇”
[Fe4S4(SPh)4]2-结构
F e
S
S
F e
F e
S
F e
S
Fe4S4基本单元生物体内的电子转移反应
Fe4S43++e-? Fe4S42+ +e-? Fe4S4+
Fe33+,Fe2+ /Fe23+,Fe22+ / Fe3+,Fe32+
Fe4S*4Cys4 n-
Schematic structures
(A) a proposed 6-Fe cluster
in [Fe]-hydrogenase,
(B) the binuclear site in D,
gigas hydrogenase,
(C) the P cluster of
nitrogenase (Rees),
(D) the P cluster of
nitrogenase (Bolin),
(E) the cofactor cluster of
nitrogenase,
(F) [MFe4S6(PEt3)4Cl] (M=
V,Mo).
二,金属 -金属多重键 (multi-bonds)
1935年,C,Brosset
K3W2Cl9 中,W—W 240pm (2.40?)
W单质中,W—W 275pm
1975年 F,A,Cotton,
Re2Cl82– (d4) Re—Re 224pm
W W
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
F,A,Cotton,
―Highlights From Recent Work On Metal -Metal Bonds‖
Inorg,Chem,39(1998)5710-5720
d3
C rCrC C
N N
B o n d B o n dR a t i o R a t i o
0,7 8 3
0,7 8 6
0,7 6 7
0,8 0 7
0,8 4 8
Mo Mo
Re Re
多重键缩短比 (多重键键长 /单键键长 )
Re Re
C lC l C l
C l
C l
C l
C l
C l
Re2Cl82– Cr2Ac4.2H2O
四方棱柱构形
C r C r O H 2H 2 O
O
C
O
C H 3
5个 d轨道的形成的 1?个 2?个 2个?键
dx2-y2轨道和 dxy的形成 2个?键四方棱柱 M-M间的 d 轨道能级图
*
*
*
M2L8四方棱柱 的 d轨道能级图
[Re2Cl8]2-+ PR3?
2?4?2 (4级键）
1,2,7-Re2Cl5(PMe3)3
2?4?2?*1 (3.5级键）
1,3,6,8-
Re2Cl4(PMe3)4+Cl2?
2?4?2?*2 (3级键）
1,3,6-Re2Cl5(PMe3)3
2?4?2?*1 (3.5级键）
[Re2Cl8]2- + PMe3 (惰性气氛，苯溶剂）?1,2,5,7-Re2Cl6(PMe3)4
(+3) (+3)
2?4?2 (4级键）
Re—Re 3.8486? 不存在金属 -金属键
(+3) (+4)
[Re2Cl8]2-+ PEt2H ( HCl，苯 ）? 1,2,5,6-Re2Cl4(?-PEt2)(PEt2H)4
Trinuclear complexes
di-2-pyridylamine (dpa-)
[Cr3(dpa)4Cl2]+
从高度对称到非对称一维导体（分子导线）
由 Pt的 5dz2轨道重叠形成导带
Pt(CN)4n-的链状分子讨论,K2Pt(CN)4的电导很小,Pt被部分氧化后电导增大，原因？
四氰基铂酸钾 K2Pt(CN)4X0.3 （ KCP）
配合物 Pt的价态
Pt?Pt间距 /pm
颜色 导电性
/1.cm?1
金属 Pt
K2Pt(CN)4?3H2O
K2Pt(CN)4Br0.3?3H2O
K2Pt(CN)4Cl0.3?3H2O
K1.75Pt(CN)4?1.5H2O
Cs2Pt(CN)4(FHF)0.39
0
+2.0
+2.3
+2.3
+2.25
+2.39
277.5
348
288
287
296
283
金属白色青铜色青铜色青铜色金色
~9.4?101
5?10?7
4-830
~200
~70-100
未知阴离子堆垛结构的四氰基铂酸盐
Cu—Cu ~ 2.44-2.81?
r(Cu2+) ~ 0.6-0.8?
Cu—Cu间 无化学键,
磁性具有强温度相关性
eff = ~ 1.4BM/Cu atom
A.F,Cotton
Adv,Inorg,Chem,(1999).
p.870
Cu2(CH3COO)4.2H2O，是否存在 Cu—Cu间的?键？
Binuclear complexes,I,Electronic structure of copper acetate,
Forster,Leslie S.; Ballhausen,C,J,Univ,Copenhagen,Acta
Chemica Scandinavica (1962),16 1385-92,CODEN,
ACHSE7 ISSN,0904-213X,Journal written in English,
CAN 57:73457 AN 1962:473457 CAPLUS
Abstract
Electronic structure of the dimeric Cu acetate Cu2(Ac)4.2H2O
was considered by using a tentative mol,orbital scheme,A
rather strong s bond exists between the 2 Cu units,in contrast
to a former proposal of a d bond (Figgis and Martin,CA 51,
1672h),Although the proposed model gives a satisfactory qual,
account of the exptl,data (antiferromagnetism,absorption
spectrum,and g factors),alternative models may also be
consistent with the rather limited data,
Dinuclear copper(II) acetate monohydrate,Redetermination of the
structure by neutron-diffraction analysis,Brown,George M.;
Chidambaram,R,Chem,Div.,Oak Ridge Natl,Lab.,Oak Ridge,
TN,USA,Acta Crystallographica,Section B,Structural
Crystallography and Crystal Chemistry (1973),29(Pt,11),2393-
403,
Abstract
The crystal structure of dinuclear Cu(II) acetate monohydrate,
Cu2(O2CCH3)4.2H2O (van Niekerk and Schoening,1953),was
refined by the full-matrix least-squares method using 3-dimensional
neutron data and revised cell parameters [a 13.167 (4),b 8.563 (2),c
13.862 (7),ANG.,b 117.019 (2)° (lCu Ka1 = 1.54051,ANG.),space
group C2/c,and Z = 4],A reasonable description of the Me groups,
which are in large-amplitude torsional oscillation,was obtained by
using a special model,R(F) = 0.061 and R(F2) = 0.072 for F2 >?,
excluding the very weak reflections and reflections mildly affected
by extinction,The intramolecular Cu-Cu vector is 2.6143 (17),ANG,
long and oriented almost exactly as reported from measurements of
magnetic anisotropy and electron spin resonance
Rhodium acetate dimer Rh2(OAc)4(H2O)2
Cu2(OAc)4L2 where L = pyridine or 0.5 pyrazine
Rh2(OAc)4(H2O)2中 Rh- Rh的键级是多少？
