A Consistent Approach to One Coordinate Pnictide Moieties M≡Pn − Using PnH 2 − Salts (M = Zr, Ti; Pn = P, As, Sb).

Abstract Establishing a congruent approach to delivering a pnictide atom (Pn 3− = P, As, and Sb) to transition metal ions is a challenge, especially for the heavier congeners As and Sb, and when varying the transition metal. We showcase here a convenient route to molecular forms of one coordinate stibide ligands bound to Zr IV and Ti IV ions, represented by the discrete salts [K(L)][(PN) 2 M≡Sb] (M = Zr ( 2 ), Ti ( 10 ); PN − = (N‐(2‐P i Pr 2 ‐4‐methylphenyl)‐2,4,6‐Me 3 C 6 H 2 ; L = 2,2,2‐Kryptofix or 18‐C‐6 crown‐ether/2THF), which were prepared via H 2 extrusion from [K(18‐C‐6)(THF)SbH 2 ] added to the Zr IV cyclometallated‐hydride, [(PN)(PN’)Zr(H)] ( 1 ), and the Ti II precursor [K(18‐C‐6)][(PN) 2 TiCl] ( 8 ) respectively. This strategy was extended to the lighter congeners Pn = As, P using [K(18‐C‐6)(THF)AsH 2 ] (M = Zr ( 3 )), and NaPH 2 (M = Ti ( 6 )). Structural and computational studies were applied to understand the bonding trends in the pnictide series, and the role of the metal ion.