Azametalla‐ closo ‐dodecaboranes

The azaborate K 2 [ nido ‐NB 10 H 11 ] is gained from nido ‐NB 10 H 13 and K[BHEt 3 ] in a 1:2 ratio. The anion [NB 10 H 11 ] 2− , which is isoelectronic with [C 2 B 9 H 11 ] 2− , reacts with [{η 6 ‐(C 6 R 6 ) · RuCl 2 } 2 ] (R = H, Me), [{η 5 ‐(C 5 Me 5 )RhCl 2 } 2 ], or [Ni(PPh 3 ) 2 Cl 2 ] to give the azametalla‐ closo ‐dodecaboranes MNB 10 H 11 with M = (C 6 Me 6 )Ru ( 2 ), (C 6 H 6 )Ru ( 3 ), (C 5 Me 5 )Rh ( 4 ), and (Ph 3 P) 2 Ni ( 5 ), respectively. The azametallaborane K[Co(NB 10 H 11 ) 2 ] ( 6 ), which contains a sandwich‐type coordinated Co atom, is formed from K 2 [NB 10 H 11 ] and CoCl 2 . The structure of 2 · CH 2 Cl 2 was determined by X‐ray diffraction. The products 2 – 6 can be derived from the icosahedral anion [B 12 H 12 ] 2− on replacing a BH 2− moiety by the isoelectronic nitrene NH and a BH moiety by the isolobal metal‐complex fragment M. The N atom is six‐coordinated in the cluster skeletons 2 – 6 .