Macropolyhedral Chalcogenaboranes: Insertion of Selenium into the Isomers of B₁₈H₂₂

High yields of novel macropolyhedral selenaboranes are reported. Reactions of the monoanions of the syn- and anti-isomers of B₁₈H₂₂ with powdered selenium in THF variously give new macropolyhedral selenaboranes: 19-vertex [SeB₁₈H₁₉]^- anion 1, 19-vertex [SeB₁₈H₂₁]^- anion 2, 20-vertex [Se₂B₁₈H₁₉]^- anion 3, and 19-vertex [Se₂B₁₇H₁₈]^- anion 4. Single-cluster [hypho-Se₂B₆H₉]^- anion 5 and neutral arachno-Se₂B₇H₉ 6 also result. All of the macropolyhedrals 1, 2, 3, and 4 are characterized by NMR spectroscopy and mass spectrometry, and by single-crystal X-ray diffraction analyses. Anions 1 and 2 each consist of an 11-vertex subcluster joined by a common two-boron edge to a 10-vertex subcluster. Anion 3 consists of an 11-vertex subcluster joined by a common boron atom and an interboron link to an arachno-type 10-vertex subcluster. Unusually, anion 3 incorporates a hexagonal pyramidal intracluster structural motif in its 11-vertex subcluster. Anion 4 entails two arachno-type 10-vertex subclusters joined by a common boron atom, and with an additional intercluster boron-boron link. NMR data for syn-B₁₈H₂₂ and its mono- and dianions 7 and 8 and single-crystal X-ray diffraction results for these anions and also the monoanion 9 of anti-B₁₈H₂₂ are also reported. The oxaborane [μ-(8,9)-O-syn-B₁₈H₂₀]^2- dianion 10 was serendipitously formed during the work and also characterized by a single-crystal X-ray diffraction study. Experimental NMR and structural findings are supported by DFT calculations throughout.