Stannylenes based on pyrrole-phosphane and dipyrromethane-diphosphane scaffolds: syntheses and behavior as precursors to PSnP pincer palladium(ii), palladium(0) and gold(i) complexes

Abstract

2-Ditertbutylphosphanylmethylpyrrole (H₂pyrmP^tBu₂) and 2,2′-bis(diisopropylphosphanylmethyl)-5,5′-dimethyldipyrromethane ((HpyrmPⁱPr₂)₂CMe₂) have been used to synthesize new P-donor-stabilized stannylenes in which the Sn atom is attached to one, SnCl(HpyrmP^tBu₂) (1) and Sn{N(SiMe₃)₂}(HpyrmP^tBu₂) (2), or two pyrrolyl-phosphane scaffolds, Sn(HpyrmP^tBu₂)₂ (3), or to a dipyrromethane-diphosphane scaffold, Sn(pyrmPⁱPr₂)₂CMe₂ (4). It has been found that stannylenes 3 and 4 are excellent precursors to transition metal complexes containing PSnP pincer-type ligands. Their reactions with chlorido transition metal complexes have afforded [PdCl{κ³P,Sn,P-SnCl(HpyrmP^tBu₂)₂}] (6), [PdCl{κ³P,Sn,P-SnCl(pyrmPⁱPr₂)₂CMe₂}] (7) and [Au{κ³P,Sn,P-SnCl(HpyrmP^tBu₂)₂}] (8), which contain a PSnP pincer-type chloridostannyl ligand. While complexes 6 and 7 are square-planar palladium(II) complexes, compound 8 is an uncommon gold(I) complex having a T-shaped coordination geometry with a very long Sn–Au bond (3.120 Å). The T-shaped palladium(0) complex [Pd{κ³P,Sn,P-Sn(pyrmPⁱPr₂)₂CMe₂}] (9), which contains an unprecedented PSnP pincer-type stannylene that behaves as a Z-type (σ-acceptor) ligand, has been prepared from 4 and [Pd(η³-C₃H₅)(η⁵-C₅H₅)].