Computational and experimental investigation of phosphaalkenyl germylenes from donor-acceptor perspective

Synthesis and Characterization of a Novel Bis‐Sulfoxide and Its Evaluation as a Ligand in p‐Block Chemistry

“…In the 13 C NMR spectrum of the stannylene 5 the signals situated at 169.7 and 170.1 ppm (in CDCl 3 ) are characteristic for the ipso C1 atom of a group 14 metallylene. [40,42,59] The formation of product 5 was also confirmed by the 119 Sn NMR with the appearance of a sharp signal at 75 ppm and a broad one at 54 ppm. This is in agreement with the results previously observed in the case of the sulfone-sulfoxide stannylene, [43] where signals were seen at 49.3 and 72.5 ppm.…”

“…Considering that the stabilization of group 14 metallylenes with different type of ligands is a continuing interest for our group, [51][52][53][54][55][56][57][58][59] we evaluated the O,C,O pincer-type ligand behaviour of bis-sulfoxide 2 towards Sn(II). In this respect, lithium derivative 3 was treated with SnCl 2 at low temperature, and the formation of the bis-sulfoxide stannylene [2,6-(para-tolylsulfinyl)-4-tert-butyl-phenyl-chlorostannylene] 5 was confirmed by 1 H NMR spectroscopy, where the disappearance of the triplet signal at 7.58 ppm for the H1 proton of the dl-isomer bis-sulfoxide 2 is observed (the signal for the H1 proton of the meso isomer at 7.50 ppm is overlapping with other signals, it's disappearance cannot be followed as clearly), as it can be seen on Figure S9 in ESI.…”

“…The 1 H NMR spectrum for stannylene 5 shows a downfield shift of the signals for the aromatic protons in the 7.27–7.85 ppm region. In the 13 C NMR spectrum of the stannylene 5 the signals situated at 169.7 and 170.1 ppm (in CDCl 3 ) are characteristic for the ipso C1 atom of a group 14 metallylene , , …”

Reactivity of Amidinatosilylenes and Amidinatogermylenes with [PtMe2(η4-cod)]: cis- versus trans-[PtMe2L2] Complexes and Cyclometalation Reactions

“…While the silylene ligands of trans-2 Si-Mes present an approximate syn conformation around the Pt atom, the germylenes of cis-2 Ge-Mes minimize their steric interactions being disposed in an approximate anti conformation. Both lengths Pt−Si (avg 2.317(5) Å; trans-2 Si-Mes ) and Pt−Ge (avg 2.399(6) Å; cis-2 Ge-Mes ) are over the top limit of the range of Pt−Si distances (2.208(2)−2.302(2) Å) and among the longest Pt−Ge distances (2.304(1)−2.409(1) Å) known for the few previously reported XRD-characterized platinum complexes equipped with terminal silylenes 15 and germylenes, 16 reflecting the large steric bulk of the 1 E-Mes ligands. The large size of the germylene ligands of cis-2 Ge-Mes also accounts for the small C Me −Pt−C Me bond angle of cis-2 Ge-Mes (avg 17 84.5(2)°).…”

Palladium and Ruthenium Derivatives Stabilised by bis-Sulfone Ligand

“…Among the large variety of ligands used for these complexes are for example different phosphines, [15] sulfoxides, [16] Schiff bases [17] or pincer ligands. [13,14,[18][19][20] Furthermore, the preparation of ligands with properties modulated by the presence of several functional groups like: metallylenes, [21][22][23] oxathia-derivatives, [24] germil-aminophosphoric esters, [25] phophaalkenyl derivatives [26][27][28] or organometallic halogenated derivatives [29][30][31] as well as their study for the stabilization of transition metals derivatives of palladium, ruthenium, gold, tungsten, etc., is a continuous concern in our team.…”