Abstract
The first fully characterized boron-functionalized heptaphosphide Zintl cluster, [(BBN)P(7)](2-) ([1](2-)), is synthesized by dehydrocoupling [HP(7)](2-). Dehydrocoupling is a previously unprecedented reaction pathway to functionalize Zintl clusters. [Na(18-c-6)](2)[1] was employed as a transition metal-free catalyst for the hydroboration of aldehydes and ketones. Moreover, the greenhouse gas carbon dioxide (CO(2)) was efficiently and selectively reduced to methoxyborane. This work represents the first examples of Zintl catalysis where the transformation is transition metal-free and where the cluster is noninnocent.