Sodium Tetra-tert-butylcyclopentaphosphanide: Synthesis, Structure, and Unexpected Formation of a Nickel(0) Tri-tert-butylcyclopentaphosphene Complex

The Versatile Reactivity of cyclo‐(P5tBu4)− with Complexes of the Nickel Triad

“…Reactions of 1 with [NiCl 2 (PR 3 ) 2 ] (PR 3 =PEt 3 , PPh 3 ), [NiCl 2 (bipy)] (bipy=2,2′‐bipyridine), [PdCl 2 (PR 3 ) 2 ] (PR 3 =PMe 2 Ph, PPh 3 ) and [PtCl 2 (PPh 3 ) 2 ] : The reaction of Na[ cyclo ‐(P 5 t Bu 4 )]8 with phosphane complexes of the nickel triad is markedly dependent on the nature of the starting material and the transition metal.…”

“…Thus, complexes with alkylphosphanes, such as [NiCl 2 (PEt 3 ) 2 ]11 and [PdCl 2 (PMe 2 Ph) 2 ],12 react with 1 with elimination of t BuCl and formation of the corresponding metal(0) cyclopentaphosphene complexes [Ni{ cyclo ‐(P 5 t Bu 3 )}(PEt 3 ) 2 ] ( 2 )8 and [Pd{ cyclo ‐(P 5 t Bu 3 )}(PMe 2 Ph) 2 ] ( 3 ; Scheme ). The formation of cyclo ‐(P 5 t Bu 4 H),13 which results from the reaction of 1 and t BuCl, is also observed in these reactions 8. The Pd complex 3 is unstable in solution and decomposes slowly, even at −27 °C, over 12 months with formation of black palladium metal and { cyclo ‐(P 4 t Bu 3 )P t Bu} 2 .…”

“…Thus, the alkali metal compounds K[ cyclo ‐(P 3 t Bu 2 )],3 K[ cyclo ‐(P 5 Ph 4 )]5 and Li[ cyclo ‐(P n t Bu n −1 )] ( n =3–5)6, 7 were obtained only in inseparable mixtures, and characterised by 31 P NMR spectroscopy. Recently we reported the targeted high‐yield synthesis of Na[ cyclo ‐(P 5 t Bu 4 )] and preliminary results on its use in coordination chemistry8, 9 and main group chemistry 10…”

“…Different reactivity patterns are observed in reactions with 1 . While the cyclo ‐(P 5 t Bu 4 ) ligand stays intact in the reaction of 1 with Et 2 AlCl10 or [RhCl(PPh 3 ) 3 ],9 elimination of t BuCl with formation of a nickel(0) cyclopentaphosphene complex is observed in the reaction with [NiCl 2 (PEt 3 ) 2 ] 8. With SnCl 2 , PbCl 2 or BiCl 3 , a redox reaction occurs with formation of the two structural isomers { cyclo ‐(P 5 t Bu 4 )} 2 and { cyclo ‐(P 4 t Bu 3 )P t Bu} 2 (besides other cyclic phosphanes) and elemental metal 10…”

Syntheses and structures of [Me2Si{As(PtBu)3}2] and [(CyP)3SiMe2] (Cy=cyclohexyl, C6H11)

“…201 kJ mol À1 ) [5]. The phosphorus counterparts [( t BuP) 4 P] À have been obtained by the in situ reactions of t BuPCl 2 and PCl 3 with Na metal in THF (Scheme 2) [6].…”