Natriumtetra-tert-butylcyclopentaphosphanid – Synthese, Struktur und unerwartete Bildung eines Nickel(0)-tri-tert-butylcyclopentaphosphen-Komplexes

Coordination Chemistry of the cyclo‐(P5tBu4)− Ion: Monomeric and Oligomeric Copper(I), Silver(I) and Gold(I) Complexes

“…Compound 1 ,6 [CuCl(PCyp 3 ) 2 ],11 [CuCl(PPh 3 ) 3 ],23 [AgCl(PPh 3 ) 2 ],24 and [AuCl(PPh 3 )]25 were prepared according to the literature procedures. [AgCl(PCyp 3 )] 4 and [AuCl(PCyp 3 )] were prepared in situ by adding 1.1 equiv of PCyp 3 to solutions of [AgCl(PPh 3 ) 2 ] and [AuCl(PPh 3 )], respectively.…”

“…5 We recently embarked on a systematic study of the syntheses, structural properties and reactivities of oligophosphanide anions with the specific aim of exploring their utility as building blocks for phosphorus‐rich metal complexes. The high‐yield synthesis and full characterisation of the sodium salt [Na{ cyclo ‐(P 5 t Bu 4 )}] ( 1 ) and its use to prepare the unusual nickel cyclopentaphosphene complex [Ni( cyclo ‐P 5 t Bu 3 )(PEt 3 ) 2 ] were early breakthroughs in this project 6. Subsequent transmetallation reactions of 1 with various halides of the nickel triad revealed its ability to form a structurally diverse class of complexes with Ni, Pd and Pt 7.…”

Synthesis and Thermolysis of the Homoleptic Iron(II) Complex [Fe{cyclo‐(P5tBu4)}2]

“…single bond 220.6(2)–224.1(3) pm),22 and short P–P bonds were observed for P1–P5 and P4–P5 (212.58(5) and 215.88(5) pm, respectively), indicating multiple‐bond character 23. Similarly, the shortest P–P distance of 213.2(1) pm in 1 was also explained by delocalisation of the lone pair of electrons at the anionic phosphorus atom into lower unoccupied orbitals (negative hyperconjugation)25 at the neighbouring phosphorus atom 13…”

“…The melting point was determined in a sealed capillary under nitrogen and is uncorrected. Na[ cyclo ‐(P 5 t Bu 4 )]13 and [FeBr 2 (CO) 4 ]25 were prepared as described in the literature.…”

“…The reactions between [Na(thf) 4 { cyclo ‐(P 5 t Bu 4 )}]13 and transition metal complexes gave phosphorus‐rich transition metal complexes in which 1) the cyclo ‐(P 5 t Bu 4 ) – ring stays intact, as in [M{ cyclo ‐(P 5 t Bu 4 )} 2 ] (M = Pd, Ni),14 [Rh{ cyclo ‐(P 5 t Bu 4 )}(PPh 3 ) 2 ]15 and [Au{ cyclo ‐(P 5 t Bu 4 )}(PCyp 3 )],16 2) formation of cyclo ‐(P 5 t Bu 3 ) occurs with elimination of t BuCl, e.g., [Ni{ cyclo ‐(P 5 t Bu 3 )}(PEt 3 ) 2 ]13 or 3) rearrangement to [{ cyclo ‐(P 4 t Bu 3 )}P t Bu] – occurs, which shows different bonding modes, for instance, bidentate chelating in [PtCl{ cyclo ‐(P 4 t Bu 3 )P t Bu}(PMe 2 Ph)],14 bis‐bidentate chelating in [Mn 2 (μ‐Br){ cyclo ‐(P 4 t Bu 3 )P t Bu}(CO) 6 ]17 and bridging (via the exocyclic P t Bu group) in [M 4 { cyclo ‐(P 4 t Bu 3 )P t Bu} 4 ] (M = Cu, Ag, Au) 18. Herein we report the first iron(II) complex [Fe{ cyclo ‐(P 5 t Bu 4 )} 2 ] ( 2 ) in which two cyclo ‐(P 5 t Bu 4 ) – ligands exhibit tridentate coordination to the iron atom thus forming an 18‐electron complex.…”