Syntheses, Characterizations, and Crystal Structures of β‐Diketiminato Compounds of Pentafluorophenyl Group 12 Derivatives, HC{[C(Me)N(C₆H₃‐2, 6‐i‐Pr₂)]₂}MC₆F₅ (M = Zn, Cd)

Abstract

The reactions of H2C[C(Me)N(C6H3‐2, 6‐i‐Pr2)]2 ((DPP)2NacNacH) and Zn(C6F5)2 · 2 EtCN or Cd(C6F5)2 · 2 MeCN in a molar ratio of approximately 1:1 selectively gave the derivatives (DPP)2NacNacMC6F5 (M = Zn, Cd) in excellent yields. No reaction was observed between (DPP)2NacNacH and Hg(C6F5)2 under similar conditions. Reactions with Hg(C6F5)OCOMe yielded the products of dismutation, Hg(C6F5)2 and Hg(OCOMe)2. (DPP)2NacNacZnC6F5 crystallises as a 1:1 adduct with THF with two independent molecules per unit cell (triclinic, P1 (no. 2)). The zinc atom is tetrahedrally surrounded by the chelating ligand, the pentafluorophenyl group and one THF molecule. A similar situation is found in the 1:1 adduct of (DPP)2NacNacCdC6F5 and DMF (monoclinic, P21/n (no. 14)), while in the donor‐free compound (CDCl3 and H2O co‐crystallize) the cadmium atom is nearly ideally trigonal planar co‐ordinated (orthorhombic, Pbnm (no. 62)).

(β‐Diketiminato)cadmium Bis(trimethylsilyl)amide: Facile Access to Low‐Coordinate Cadmium Complexes

“…A distorted trigonal‐planar geometry is observed at the cadmium atom, with the two β‐diketiminate nitrogen atoms forming an N1–Cd–N2 bite angle of 90.08(6)°, smaller than the bite angle observed in the four‐coordinate complex [(BDI)Cd(µ‐I) 2 Li(OEt) 2 ] (91.46°)[2b] yet larger than the bite angle of the methylcadmium complex [(BDI)CdMe] (88.45°). [1b] The cadmium–amide bond Cd–N3 [2.0892(16) Å] is shorter than that reported for the only other structurally characterised monometallic cadmium–HMDS complex, [{C(py) 3 }Cd(HMDS)] (2.104 Å; py = pyrazoyl) …”

“…This has been partly due to the lack of available routes to suitable precursors that are easy to derivatise. Three‐coordinate (β‐diketiminato)cadmium complexes have been successfully synthesised from highly toxic organocadmium complexes . However, attempts at generating homometallic (β‐diketiminato)cadmium iodide from the more benign CdI 2 salt results in incomplete salt metathesis, yielding a variety of cadmium/lithium heterodimetallic complexes (Figure ) .…”

An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides

“…The Zn−N py‐Me bond length is 2.157(5) Å and the coordination of py‐Me results in slight elongation of the Zn−C bond (2.005(5) Å, as opposed to 1.964(4) in 1 ). We note that complexes of the type ( dipp BDI)ZnR do not show pronounced coordination in strong donating solvents and there is only a handful of examples of the respective well‐defined Lewis acid–base adducts . The alkylperoxide 4 crystallizes in the space group P as a monomer with four‐coordinate zinc center adopting a severely distorted tetrahedral geometry (Figure ).…”

“…We note that complexes of the type ( dipp BDI)ZnR do not show pronounced coordination in strong donating solvents [58] and there is only ahandful of examples of the respective well-defined Lewis acid-base adducts. [59] Thealkylperoxide 4 crystallizes in the space group P1 as am onomer with four-coordinate zinc center adopting as everely distorted tetrahedral geometry (Figure 1). The alkylperoxide O À Ob ond length (1.473 (7) )i n4 is slightly longer than that observed in the dimeric ethylperoxide 2 2 (1.451 (2) ).…”

I. Synthesis and Reactivity of Novel β-Diketiminato-cadmium Complexes, II. Synthesis of Lead Selenide Nanoparticles for Use in Solar Cells

“…[(BDIDIPP)Cd(C6F5)] XXXIII was synthesised in very good yields, upon the addition of BDIDIPP-H to a solution of [Cd(C6F5)2•2MeCN]. 24 Two separate crystal structures were obtained by varying the crystallisation conditions (Figure 8).…”