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CH2405 - Multi-Nuclear Metal Species (SJP)

CH2405 - Multi-Nuclear Metal Species (SJP)

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CH2405
 –
Multinuclear Metal SystemsBond Order in Multinuclear Metal SystemsTypically bond order is considered to equate to the number of bonding electrons minus the numberof anti-bonding electrons divided by 2. In metal systems this is not always true, orbital overlapcontribution from
σ orbitals is stronger than for π orbitals, which are in turn stronger than for δ
 orbitals, the result of this is a bond order that is often smaller than calculated. Bond strength wouldbe expected to increase down a group however it is not always this straightforward, for exampleW
24+
is sensitive to oxidation, in other words the bond strength can also depend on the equilibriumbetween M
24+
and 2M
2+
.A Few Historical Examples of Metal-Metal Bonds
1840
; Chromium acetate [Cr
2
(OAc)
4
].2H
2
O
Synthesis;
[Cr
II
(H
2
O)
6
]
2+

 
[Cr
2
(OAc)
4
].2H
2
OThe hexaaqua species is blue with chromium in the high spin d
4
configuration, compared tochromium acetate which is red and diamagnetic, therefore containing no unpaired electrons.
1957;
Decacarbonyl dimanganese Mn
2
(CO)
10
1964;
Octachloride dirhenium [Re
2
(Cl)
8
]
2-
 This species contains a Re-Re quadruple bond.
Synthesis;
[ReO
4
]
-
+ HCl + H
3
PO
4
+ Cs
+
 
Cs
2
[Re
2
(Cl)
8
]
 Alternative synthesis;
2[NBu
4
][ReO
4
] + 8PhCOCl
[Re(Cl)
8
][NBu
4
]
2
 This method utilises NBu
4
to facilitate solubility in organic solvents, the benzoyl chloride acts as areducing agent, chlorinating agent and organises the Re units through the formation of anintermediate containing a benzoate bridge motif.
Figure 1 - Benzoate bridging motif 
Criteria for a Metal-Metal BondIn order to form a metal-metal bond there must be orbitals capable of overlapping with theappropriate size, orientation and energy. Since 5d orbitals are more diffuse than 4d and 3d orbitalsthey are capable of forming better overlap and so metal-metal bonds between atoms with 5dorbitals will be stronger than those between 3d/4d orbitals(Table 1).
 
Table 1 - Analagous group VII complexes and the relative first excitation energies
Complex E (
σ
-
σ
*)Mn
2
(CO)
10
29740 cm
-1
 
Tc
2
(CO)
10
32400 cm
-1
Re
2
(CO)
10
32800 cm
-1
Multiple Metal-Metal Bonds
Table 2 - Electron configurations and the subsequent bond multiplicities
d
1
-d
1
Single bond
 
d
2
-d
2
 
Double bond
d
3
-d
3
 
Triple bond
d
4
-d
4
 
Quadruple bond (Optimum)
d
5
-d
5
 
Triple bond
d
6
-d
6
 
Double bond
d
7
-d
7
 
Single bond
d
8
-d
8
 
No bond (due to symmetry interactions)-[Re
2
(Cl)
8
]
2-
 The structure of this species(Figure 2)consists of two pseudo-square planar ReCl
4
units bound in aneclipsed formation. The chlorine atoms are within double the Van der Waals distance and sostearically this arrangement is disfavoured, the Re-Re bond must therefore be highly energeticallyfavoured to account for this seemingly flawed structure. In rhenium metal the average Re-Re bonddistance is approx. 2.78Å and so the distance of 2.24Å in this species is telling of multiply bondedmetal atoms.
Figure 2- The structure of [Re
2
Cl
8
]
2-
 
By treating each ReCl
4
unit individually and applying a Jahn-Teller style distortion along the z-axis,Figure 3is reached. This diagram shows that the overall bond order is calculated as 4, and can bedescribed in terms of the nature of the bonding overlap in the form
σ
2
π
4
δ
2
. This species actually hasa measured bond order of 3.25.
 
 Reactions of [Re
2
Cl
8
]
2-
 
Retaining the quadruple bond;
i) Halide exchange;[Re
2
Cl
8
]
2-
+ Bu
4
NX

[Re
2
X
8
]
2-
 ii) Other anions;[Re
2
Cl
8
]
2-
+ H
2
SO
4
 
[Re
2
(SO
4
)
4
]
2-
 Here the SO
4
units bridge the Re-Re system and force the Re-Re atoms even closer together with abond distance of 2.14Å.iii) Partial substitution by
 –
PR
3
 [Re
2
Cl
8
]
2-
+ 2PMePh
2
 
[Re
2
Cl
6
(PMePh)
2
]The structure of this species has one PR
3
unit at each Re, trans to each other due to stearicinteractions.
Deviations from a calculated bond order of 4;
i) Reactions with dithioethers[Re
2
Cl
8
]
2-
+ MeS(CH
2
)
2
SMe
[Re
2
Cl
5
(MeS(CH
2
)
2
SMe)
2
]
 
d
xy
d
xy
d
xz,
d
yz
d
xz,
d
yz
d
z2
d
z2
Figure 3 - MO diagram for [Re
2
(Cl)
8
]
2-
 

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