I previously determined that if $\mathfrak{sl}$ denotes the Lie algebra of $SL_2(\mathbb C)$ and $\mathfrak o$ denotes the Lie algebra of $O(3,\mathbb C)$ then a basis for $\mathfrak{sl}$ is given by
$$ b_1 = \begin{pmatrix}0 & 1 \\ 0 & 0 \end{pmatrix} \text{ and } b_2 = \begin{pmatrix}0 & 0 \\ 1 & 0 \end{pmatrix}, b_3 = \begin{pmatrix}1 & 0 \\ 0 & -1 \end{pmatrix} , ib_1, ib_2, ib_3$$
and a basis for $\mathfrak o$ is given by
$$ B_1 = \begin{pmatrix} 0 & 1 & 0 \\ 0 & 0 & 0 \\ 0 & 0 & 0\end{pmatrix}, B_2 = \begin{pmatrix} 0 & 0 & 0 \\ 0 & 0 & 1 \\ 0 & 0 & 0\end{pmatrix}, B_3 = \begin{pmatrix} 0 & 0 & 1 \\ 0 & 0 & 0 \\ 0 & 0 & 0\end{pmatrix}, iB_1, iB_2, iB_3$$
It is my goal to prove that $\mathfrak{sl}$ and $\mathfrak o$ are isomorphic.
My idea is to define what values a map $\varphi: \mathfrak{sl}\to \mathfrak o$ takes on the basis elements. By trial and error I found that the following assignment
$$ b_i \mapsto B_i, ib_i \mapsto iB_i$$
satisfies $[\varphi(b_1),\varphi(b_2)] = B_3 = \varphi([b_1,b_2])$ and $[\varphi(ib_1),\varphi(ib_2)] = iB_3\varphi([ib_1, ib_2])$.
My main question is: is there a way to prove that is satisfies the bracket relation for the other basis elements without doing all the other computations?
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My other question is: is my work correct?
(1) Presumably you are looking for a isomorphism $\mathfrak{sl}(2, \mathbb{C}) \stackrel{\cong}{\to} \mathfrak{o}(3, \mathbb{C})$ as complex Lie algebras, which means in particular that we think of the vector spaces underlying the two Lie algebras as complex. (It's conventional to write the latter Lie algebra here as $\mathfrak{so}(3, \mathbb{C})$) As such, the two given lists of vectors are not bases, as, e.g., $b_1$ and $ib_1$ are scalar multiples of one another, and $\{b_1, b_2, b_3\}$ is a basis for $\mathfrak{sl}(2, \mathbb{C})$.
(2) The matrix Lie algebra spanned by the matrices $B_1$, $B_2$, and $B_3$ is not a copy of $\mathfrak{o}(3, \mathbb{C})$---one way to see this is to note that the Lie algebra they span is nilpotent, whereas $\mathfrak{o}(3, \mathbb{C})$ is semisimple. The usual representation of $\mathfrak{o}(3, \mathbb{C})$ is as the matrix Lie algebra of skew-symmetric $3 \times 3$ matrices.
(3) There are certainly invariant/noncomputational ways to approach the problem, and Qiaochu's answer describes one efficient method. But note that with only three basis elements, one need only verify that a candidate isomorphism $\varphi$ respect just three brackets, e.g., $[b_2, b_3]$, $[b_3, b_1]$, $[b_1, b_2]$.