Synthesis and Reactivity of a Mono‐Coordinated Triplet Bismuthinidene

Abstract

Abstract The triplet bismuthinidene Ar*Bi ( 4 ) stabilized by a very bulky septiphenyl ligand (Ar* = 3,5‐ i ‐Pr 2 ‐2,6‐(2,6‐Me 2 ‐3,5‐(2,6‐ i ‐Pr 2 C 6 H 3 ) 2 –C 6 H)–C 6 H) was synthesized by dehydrogenation of in situ formed bismuth dihydride Ar*BiH 2 ( 3 ). Oxidative addition reactions of 4 with alkyl halides (MeI, EtBr, i ‐PrBr) yielded bismuthanes Ar*Bi(Me)I ( 5 ), Ar*Bi(Et)Br ( 6 ), and Ar*Bi( i ‐Pr)Br ( 7 ), which reacted with LiAlH 4 and LiAlD 4 to the thermally robust bismuth monohydrides Ar*Bi(R)H (R = Me 8 , Et 10 , i ‐Pr 12 ) and monodeuterides Ar*Bi(R)D (R = Me 9 , Et 11 , i ‐Pr 13 ). Ar*Bi(NMe 2 ) 2 1 and Ar*BiH 2 3 were characterized in situ by 1 H NMR spectroscopy and sc‐XRD ( 1 ), whereas the other compounds were characterized by heteronuclear NMR ( 1 H/ 2 H (D), 13 C) and IR spectroscopy, elemental analysis ( Ar*‐2 , Ar*‐3 , Ar*‐5 , Ar*‐7 , Ar*I , Ar*H , 2 , 4 − 7 ), as well as by UV–vis ( 4 ) and sc‐XRD ( Ar*‐7 , Ar*I , Ar*Li·Li t ‐Bu , Ar*H , 1 , 2 , 4 , 12 ). Quantum chemical calculations revealed the triplet character of the bismuthinidine 4 .