A “Push–Pull” Stabilized Phosphinidene Supported by a Phosphine‐Functionalized β‐Diketiminato Ligand

• Published in: Chemistry : a European journal Vol. 26; no. 41; pp. 9024 - 9031
• Main Authors: Bestgen, Sebastian, Mehta, Meera, Johnstone, Timothy C., Roesky, Peter W., Goicoechea, Jose M.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 22.07.2020; Wiley Subscription Services, Inc; John Wiley and Sons Inc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Chlorides; Germanium; Ligands; phosphaethynolate; Phosphine; Phosphines; phosphinidene; Physical Sciences; Science & Technology; Tin; tris(pentafluorophenyl)borane; β-diketimine; ELEMENT COMPOUNDS; phosphinidene; tris(pentafluorophenyl)borane; CRYSTAL-STRUCTURE; beta-diketimine; PHOSPHORUS ANALOGS; CATALYTIC PERFORMANCE; ACTINIDES ANNUAL SURVEY; COVALENT RADII; CHEMISTRY; phosphine; DIVALENT GERMANIUM; TIN-COMPOUNDS; phosphaethynolate; METAL-COMPLEXES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202001762

The use of a bis(diphenyl)phosphine functionalized β‐diketiminato ligand, [HC{(CH3)C}2{(ortho‐[P(C6H5)2]2C6H4)N}2]− (PNac), as a support for germanium(II) and tin(II) chloride and phosphaketene compounds, is described. The conformational flexibility and hemilability of this unique ligand provide a versatile coordination environment that can accommodate the electronic needs of the ligated elements. For example, chloride ion from [(PNac)ECl] (E=Ge, Sn) affords the cationic germyliumylidene and stannyliumylidene species [(PNac)E]+ in which the pendant phosphine arms associate more strongly with the Lewis acidic main group element centers, providing further electronic stabilization. In a similar fashion, chemical decarbonylation of the germanium phosphaketene [(PNac)Ge(PCO)] with tris(pentafluorophenyl)borane affords a “push–pull” stabilized phosphinidene in which one of the phosphine groups of the ligand backbone associates with the low valent phosphinidene center. The synthesis and reactivity of a family of germanium(II) and tin(II) complexes supported by a bis(diphenyl)phosphine functionalized β‐diketiminato ligand is reported, including an intramolecularly stabilized “push–pull” phosphinidene.