Synthesis and Coordination Chemistry of 3a,7a-Azaborindenyl, a New Isoelectronic Analogue of the Indenyl Ligand

Abstract

The fused-ring diheteroaromatic 3a,7a-azaborindenyl anion (1) has been prepared by a synthesis using the Grubbs ring-closing metathesis. 1 has been converted to the Cp*ZrCl2 complex 2, which closely resembles the corresponding (Ind)Cp*ZrCl2.

B3N3 Borazine Substitution in Hexa‐peri‐Hexabenzocoronene: Computational Analysis and Scholl Reaction of Hexaphenylborazine

“…[22][23][24][25] The first such compound, 9aza-10-boraphenanthrene, was synthesized by Dewar's group in 1958, [26] who subsequently investigated the properties of B/N-substituted naphthalenes, phenanthrenes, and triphenylenes. [27][28][29][30][31][32][33][34] More recently, significant contributions have been provided by Ashe and co-workers, [35][36][37] and by Piers and coworkers, [38][39][40][41][42] for polycyclic B/N-containing aromatic compounds. For example, the Piers group reported the synthesis of internally B/N-substituted pyrene, and added an example having a B 2 N 2 core to the known B/N-substituted triphenylenes.…”

Catalysis and Organometallic Chemistry of Monometallic Species

“…80 The mechanism of C-F activation of nonperfluorinated alkenes 81 ] and C 6 F 6 have also been described. 83 New ligand systems applied to group 4 include complexes of 3a,7a,-azaborindenyl, 7 an isoelectronic analogue of indenyl, 84 and a zirconium () complex of a partially hydrogenated corranulene ('buckybowl'). 85 The first structurally characterised homoleptic σ-organotitanium() complex [Ti(C 6 Cl 5 ) 4 ] Ϫ is mononuclear with T d symmetry.…”

Introduction

“…In dinuclear complexes, the odd electrons on each metal may pair up, however, as in the diamagnetic d 7 -d 7 dimer, [(OC) 5 Re−Re(CO) 5 ]. An odd d n configuration, such as d 7 (e.g., [Re(CO) 3 (PCy 3 ) 2 ]), therefore, guarantees paramagnetism if we are dealing with a mononuclear complex-one containing only a single metal atom.…”

“…If CO were bound to the metal by its carbon lone pair, nonbonding with respect to CO, then the ν(CO) frequency in the complex would differ very little from that in free CO. 5 The dipole moments of a variety of coordination compounds show that the bond moments of the M−L bonds of most σ -donor ligands are about 4 D, with the donor atom positive. Metal complexes, in contrast, show ν(CO) coordination shifts of hundreds of wavenumbers to lower energy, consistent with the weakening of the C−O bond that would be expected if the π * orbital were being filled [e.g., Cr(CO) 6 .…”