Résumé
Chapter 4, “Cyanide Compounds,” illustrates an explosively developing research theme in which the cyanide ligand is used as a linking agent for the designed assembly of polynuclear metal complexes. Syntheses of several basic building blocks, such as K
3
[Cr(CN)
6
],Cr(Me
3
tacn)(CN)
3
,K
4
[Mo(CN)
8
],Na[W(CO)
5
CN],K[CpFe(CO)(CN)
2
],[NEt
4
][Cp*Rh(CN)
3
],[Fe
4
(bpy)
8
(μ‐CN)
4
][PF
6
]
4
,. are given here. These units may be used in several ways to construct polynuclear compounds. One approach involves a hexacyanometalate core decorated with peripheral metal centers, e.g., [{Cu(tpa)(CN)}
6
Fe][ClO
4
]
8
. or [Cr{CNNi(tetren)}
6
][ClO
4
]
9
. An octacyanometalate unit can lead to higher nuclearity condensed compounds, as in [Co{Co(MeOH)
3
}
8
(μ‐CN)
30
{Mo(CN)
3
}
6
]. Alternatively, a cluster core may be substituted with cyano complexes as ligands, as in [PPh
4
]
2
[Fe
4
S
4
{NCW(CO)
5
}
4
]. If there are two cis cyano ligands on the building block, then quadrilateral or square structures often result, as in {CpFe(CO(μ‐CN)
2
Cu(PCy
3
)}
2
and [Fe
2
Cu
2
(bpy)
6
(μ‐CN)
4
][PF
6
]
4
However, if there are three adjacent cyano ligands, then cubic cages may be constructed as in [(CpCo)
4
(Cp*Rh)
4
(μ‐CN)
12
][PF
6
]
4
.