Application of the Donor–Acceptor Concept to Intercept Low Oxidation State Group 14 Element Hydrides using a Wittig Reagent as a Lewis Base

Abstract

This article outlines our attempts to stabilize the Group 14 element dihydrides, GeH2 and SnH2, using commonly employed phosphine and pyridine donors; in each case, elemental Ge and Sn extrusion was noted. However, when these phosphorus and nitrogen donors were replaced with the ylidic Wittig ligand Ph3P═CMe2, stable inorganic methylene complexes (EH2) were obtained, demonstrating the utility of this under-explored ligand class in advancing main group element coordination chemistry.

Direct Evaluation of the Quantum Confinement Effect in Single Isolated Ge Nanocrystals

“…40 We also studied ∼5.5 nm (average diameter) Ge-NCs with peripheral NMe 2 surface groups that were prepared by microwave irradiation of Ph 3 PCMe 2 ·GeH 2 ·BH 3 in the presence of 3-dimethylamino-1-propyne as a capping agent. 40,55 In addition, 8 nm (average size) 2-dodecanone-capped Ge-NCs were also investigated. These dodecanone-capped particles were prepared by microwave heating for 1 h at 190°C a mixture of Ph 3 PCMe 2 ·GeH 2 ·BH 3 precursor (30 mg, 0.076 mmol) and 5 mL of 2-dodecanone sealed in a microwave vial using a previously used workup procedure.…”

Phosphonium salts and P-ylides

“…303 Martschitsch and Schubert reported NMR studies on the reaction of [(k 2 305 Swarnakar et al investigated the stabilisation of Group 14 element dihydrides, (GeH 2 and SnH 2 ). 306 They noticed that only the ylide Ph 3 P¼CMe 2 afforded stable inorganic methylene complexes, demonstrating the utility of this under-explored ligand class. DFT calculations on ylide complexes were also reported.…”

Phosphonium salts and P-ylides

“…302 Analogous compounds were obtained by Sundermeyer and co-workers using ruthenium as the metal center. 303 Martschitsch and Schubert reported NMR studies on the reaction of [ 306 They noticed that only the ylide Ph 3 P¼CMe 2 afforded stable inorganic methylene complexes, demonstrating the utility of this under-explored ligand class. DFT calculations on ylide complexes were also reported.…”