Synthesis and Reactivity Towards Cationic Group 11 Metal Centers of an Extended Silacalix-[3]-phosphinine Macrocycle

Abstract

A synthetic route to a new type of phosphinine-based macrocycle has been developed. This approach involves the reaction of a phosphinine bearing two pendant SiMe 2 OSiMe 2 CCR (R = Ph) (5) groups with two equivalents of a diazaphosphinine (1). The 2,6-bis(azaphosphininedimethylsilyl)-phosphinine (6) formed was then reacted under dilute conditions with a second equivalent of phosphinine 5 to produce the new macrocycle 4. The X-ray crystal structure of 4 reveals no particular strain, and the macrocycle was fluxional in solution even at low temperature (−60°C). Reactions of macrocycle 4 with [Cu(MeCN) 4 ][BF 4 ], [Ag][BF 4 ] and [AuCl(-

[1L-3,4-Bis-O-(diphenylphosphino)-1,2,5,6-tetra-O-methyl-chiro-inositol-κ2P,P′][η4-(Z,Z)-cycloocta-1,5-diene]rhodium(I) tetrafluoridoborate chloroform solvate

“…Interactions between chloroform solvent molecules and tetra¯uoroborate anions similar to those reported here have also been observed [e.g. in LUBTAD (Moores et al, 2002), with HÁ Á ÁF = 2.34 A Ê and CÐHÁ Á ÁF = 171 ]. Signi®cant interactions of phenyl H atoms in the meta position with uoroborate anions (H113, H115, H313 and H315) have been noted in at least ten CSD structures since 2003.…”

2‐(Trimethylsilyl)‐λ3‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity

“…Even though the synthesis of phosphinine‐Ag(I) complexes has been documented before, no structural information of such coordination compounds has been reported in literature until now . We therefore attempted to react silyl‐phosphinine 1 with AgOTf in CH 2 Cl 2 .…”

Preparation and X-ray analyses of siloxane-bridged acyclic and 8-membered cyclic phosphaethenes

“…The 8-membered heterocycle bearing two exo-P@C bonds in 5 is an intriguing molecular motif to show attractive nature due to an interaction between the reducible phosphaalkene parts and unique coordination character [6,26] supported by disiloxy chains to conform the suitable geometries [7]. Furthermore, 3 and 4 are expected to serve as a promising intermediate to synthesize novel organophosphorus compounds, which can be employed for coordination and supramolecular chemistry.…”