Synthetic and Structural Studies of Lead and Bismuth Organohalides Bearing a β‐Diketiminato Ligand

Abstract

Two novel organohalides of lead and bismuth supported by a β-diketiminato ligand are reported. Salt elimination reactions of the β-diketiminatolithium salt and the corresponding lead and bismuth halides led to the isolation of lead [{HC(CMeNAr) 2 }PbBr] (2; Ar ϭ 2,6-iPr 2 C 6 H 3 ) and bismuth [{HC(Et 2 NCH 2 CH 2 NCMe) 2 }BiCl 2 ] (4), respectively. These new 2205 compounds have been characterized by spectrometric and elemental analyses, and the solid-state structures have been determined by single-crystal X-ray structural analysis.

Synthesis and characterization of β-diketiminate germanium(II) and tin(II) bromides

“…This is in contrast to the corresponding bromo derivatives [8]. Independently, Lappert et al and we reported on the b-diketiminate of lead(II) bromo derivative [9,10] [12] with elemental bromine. Herein we outline the preparation and characterization of the monomeric LGeBr (1) and LSnBr (2) [L = HC(CMeNAr) 2 ; Ar = 2,6-iPr 2 C 6 H 3 ] compounds.…”

The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)]2 {L = HC[(CMe)(NAr)]2, Ar = 2,6‐iPr2C6H3} and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

“…These differences are probably due to the different coordination number and the various functional groups at the Bi center. In a similar compound, L a BiCl 2 {L a = HC[(CMe)(NCH 2 CH 2 NEt 2 )] 2 }, Bi–N bond lengths of 2.232(2)–2.246(2) Å are observed 14a. The Bi–Cl terminal bonds [2.5901(12) Å in 1 , 2.453(4)–2.638(3) Å in 2 ] are shorter than the Bi–Cl bridge bonds [2.8513(12)–2.8720(15) Å in 1 , 2.671(4)–3.081(4) Å in 2 ].…”

“…Multiple coordination sites in the N‐substituents or avoidance of an active group in the backbone may have the same function. The former has been demonstrated by Roesky et al with the preparation of L a BiCl 2 ,14a and the latter by Lappert et al with the synthesis of L b 2 Bi 2 X 4 (X = Cl, Br, and I) 14b. With respect to the salt‐elimination metathesis, routine operations of removal of the salt followed by crystallization or recrystallization seem to be unworkable for obtaining pure 1 , 2 , and 4 .…”

The First Monomeric β‐Diketiminate Stabilized Four‐Coordinated Bismuth(III) Bistrifluoromethanesulfonate

“…Up to now only ten molecules of β‐diketiminate (or similar types of ligand) stabilized bismuth derivatives are known in the literature 5. The first hexacoordinated monomeric β‐diketiminate ligand with nitrogen‐based pendant arms [{HC(Et 2 NCH 2 CH 2 NCMe) 2 }BiCl 2 ] was reported by Roesky and his co‐workers in 2007 5a. Later different derivatives of penta‐ or hexacoordinated β‐diketiminate (or similar types of ligand) stabilized bismuth halides were reported.…”