Synthesis and X-ray Crystal Structure of Diimidosulfinate Transition Metal Complexes

Abstract

Bis(trimethylsilyl)sulfurdiimide S(NSiMe 3 ) 2 reacts with equimolar amounts of Me 2 Zn and Cp* 2 Zn either with insertion into the metal−carbon bond and formation of the expected S-methyl diimidosulfinate complex [MeZnN-(SiMe 3 )S(Me)NSiMe 3 ] 2 1 or the unexpected complex {Me 3 SiNS[N(SiMe 3 )-SNSiMe 3 ]N(SiMe 3 )Zn} 2 2. Insertion reactions were also observed with Cp*MMe 3 (M = Ti, Zr, Hf), yielding Cp*(Me) 2 M[Me 3 SiNS(Me)NSiMe 3 ] (M = Ti 3, Zr 4, Hf 5), whereas the corresponding Cl-substituted derivatives Cp*(Cl) 2 M[(Me 3 SiNS(Me)NSiMe 3 ] (M = Ti 6, Zr 7, Hf 8) were obtained from salt elimination reactions of Li S-methyl diimidosulfinate (Me 3 SiN) 2 S(Me)Li-(thf)] 2 9with Cp*MCl 3 . Compounds 1−8 were characterized by heteronuclear NMR ( 1 H and 13 C) and IR spectroscopy, and the solid state structures of 1−5 and 9 were determined by single crystal X-ray diffraction.

Syntheses and Structures of Homo- and Heteroleptic Beryllium Complexes Containing N,N′-Chelating Ligands

“…Homoleptic Be complexes containing N,N′-chelating substituents were synthesized by an insertion reaction of BeEt 2 with carbodiimides (C­[NR] 2 ) and sulfurdiimide S­(NSiMe 3 ) 2 , whereas analogous reactions of ZnEt 2 yielded only the heteroleptic complexes LZnEt . These findings clearly prove the increased reactivity of BeEt 2 compared to ZnEt 2 , resulting from the higher nucleophilic character of the Be-Et group compared to the Zn-Et group due to the higher bond polarity.…”

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

“…And yet, despite all the additional complexity, the FMOs will still have the expected sequence of ( n 3) 2 (π2) 2 (π3) 0 levels across the substituent classes being considered in this work, consistent with the line drawings of e. g. Figure 1. Reactivity towards either nucleophiles [6,58] or free electrons [56d] is expected at the π3/π’3 LUMOs, for which the highest coefficients are always at sulfur. At the same time, significant delocalization of both the HOMO and LUMO into the aryl π‐system will influence the redox tuning that is the topic of this work.…”