Let's find the (anti)commutator of an arbitrary [itex]2 \times 2[/itex] matrix [itex]\hat{X}[/itex] with the matrix corresponding to the operator [itex]\hbar \, \hat{s}_{z} = \frac{\hbar}{2} \, \sigma_{3}[/itex]. We get:
[tex]
\left[\frac{\hbar}{2} \, \hat{\sigma}_{3}, \hat{X} \right] = <br />
\left[\begin{array}{cc}<br />
\frac{\hbar}{2} & 0 \\<br />
<br />
0 & -\frac{\hbar}{2}<br />
\end{array}\right] \cdot \left[\begin{array}{cc}<br />
a & b \\<br />
<br />
c & d<br />
\end{array}\right] - \left[\begin{array}{cc}<br />
a & b \\<br />
<br />
c & d<br />
\end{array}\right] \cdot \left[\begin{array}{cc}<br />
\frac{\hbar}{2} & 0 \\<br />
<br />
0 & -\frac{\hbar}{2}<br />
\end{array}\right] = \hbar \, \left[\begin{array}{cc}<br />
0 & b \\<br />
<br />
-c & 0<br />
\end{array}\right][/tex]
But, this matrix has no diagonal elements, so it is never proportional to the unit matirx.
However, if you take the anticommutator, then you will get:[tex]
\left\{\frac{\hbar}{2} \, \hat{\sigma}_{3}, \hat{X} \right\} = <br />
\left[\begin{array}{cc}<br />
\frac{\hbar}{2} & 0 \\<br />
<br />
0 & -\frac{\hbar}{2}<br />
\end{array}\right] \cdot \left[\begin{array}{cc}<br />
a & b \\<br />
<br />
c & d<br />
\end{array}\right] + \left[\begin{array}{cc}<br />
a & b \\<br />
<br />
c & d<br />
\end{array}\right] \cdot \left[\begin{array}{cc}<br />
\frac{\hbar}{2} & 0 \\<br />
<br />
0 & -\frac{\hbar}{2}<br />
\end{array}\right] = \hbar \, \left[\begin{array}{cc}<br />
a & 0 \\<br />
<br />
0 & -d<br />
\end{array}\right][/tex]
Now, choosing [itex]a = -d = i[/itex], we see that:
[tex]
\left\{\hbar \, \hat{\sigma}_{3}, i \, \hat{\sigma}_{3}\right\} = i \, \hbar \, \hat{1}[/tex]
So, if we accept that for the particles with spin-1/2, the corresponding canonical relations between the operators are anticommutations, then, we might say that the conjugate variable to [itex]\sigma_{z}[/itex] is [itex]\frac{i}{\hbar} \, {\sigma}_{z}[/itex].