Synthesis and Characterization of N-[2-P(i-Pr)₂-4-methylphenyl]₂^– (PNP) Pincer Tin(IV) and Tin(II) Complexes

Abstract

N-[2-P(i-Pr)(2)-4-methylphenyl](2)(-) (PNP) pincer complexes of tin(IV) and tin(II), [(PNP)SnCl(3)] (2) and [(PNP)SnN(SiMe(3))(2)] (3), respectively, were prepared and characterized by X-ray diffraction, solution and solid state NMR spectroscopy, and (119)Sn Mössbauer spectroscopy. Furthermore, (119)Sn cross polarization magic angle spinning NMR spectroscopic data of [Sn(NMe(2))(2)](2) are reported. Compound 2 is surprisingly stable toward air, but attempts to substitute chloride ligands caused decomposition.

Spontaneous vs. Base‐Induced Dehydrochlorination of Group 14 ortho‐Carboranylamidinates

“…In accordance with the lighter homologues 8-10, the Sn-N interaction can therefore be described as a strong covalent bond. [30,31] The nature of the E-N bond in the R 2 ECl[HL]-type compounds 8-11 fits to the bonding situation within the amidinate moiety. The C3-N1 bond is in the range of a single bond, with approx.…”

“…[18] In 1-6, the E-C-(carborane) separations are comparable with those in other group 14 organyl compounds, [24][25][26][27][28][29][30] while the E-N separations are considerably larger than those observed for classical covalent E-N bonds. [26,30,31] Within the amidine fragment, the C3-N1 separation is 126-131 pm, while the C3-N2 bond is slightly longer, at 132-137 pm. Thus in the HL -ligand, the π-electron density is probably located between the amidine C atom and the coordinated N atom, and the E-N contact should be described as a secondary coordinative interaction, rather than a covalent bond.…”

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

“…Other examples are Sn(II) and Sn(IV) complexes of phosphinothiolates [315][316][317] and the PNP pincer N{C 6 H 4 (4-Me)P i Pr 2 } 2 [318], and Sn(IV) complexes of bis(phenolate)phosphines [319].…”

The role of the bis-trimethylsilylamido ligand, [N{SiMe3}2]−, in main group chemistry. Part 2: Structural chemistry of the metallic p-block elements

“…Crystallographic examination shows the solid-state structure exists as the N,N -chelate with a 5-membered metallacycle in preference to the possible 6-membered P,N-chelate. Donation of neutral phosphorus atoms was observed in the monomeric PNP pincer compound, Sn({2-(Pi-Pr 2 )-4-MeC 6 H 3 } 2 )(N{SiMe 3 } 2 ) (125), in which a tridentate coordination mode with both phosphane donor groups interacting with the tin is observed [105]. …”