Ir‐Komplexe mit P₄‐Bicyclotetraphosphan und P₈‐Cunean als Liganden – CO‐Insertion in eine Ir–P‐Bindung

Abstract

Ir Complexes with P4 Bicyclotetraphosphane and P8 Cunean as Ligands – CO Insertion into an Ir–P Bond The reaction of [Cp*Ir(CO)2] with white phosphorus under photochemical or thermal conditions produces the bicyclotetraphosphane complexes 1 and 2 and the cunean‐type complex 3. The products were characterized by NMR, IR, and mass spectroscopy as well as by X‐ray structure analyses. Complex 1 reacts with CO with insertion into a Ir–P bond to form 2 and finally [Cp*Ir(CO)2].

P5X2+ (X=Br, I), a Phosphorus-Rich Binary P−X Cation with a C2v-Symmetric P5 Cage This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. We thank Prof. H. Schnöckel for valuable discussions.

“…[23] This P 5 cage is unprecedented and is not found as part of the many polyphosphides or organopolyphosphanes known to date. [24,25] The P À P bond lengths in the P 5 Br 2 ion (2.150(7) ± 2.262(8) ä) are close to the values found in P 4 (2.21 ä) or Ag(P 4 ) 2 (2.15 ± 2.32 ä), [13] and the PÀBr distances lie in the normal range. Ab initio MP2/TZVPP [26±29] and HF-DFT MPW1PW91/6-311G(2df) [30±32] calculations reproduced the solid-state geometry of P 5 Br 2 within 0.024 ä and 1.…”

PX4+, P2X5+, and P5X2+ (X=Br, I) Salts of the Superweak Al(OR)4 Anion [R=C(CF3)3]

“…[20,21] The range of the PÀP bond lengths in the P 5 Br 2 cation of 2.150(7) to 2.262(8) ä is close to the values found in P 4 (2.21 ä) or Ag(P 4 ) 2 (2.15 ± 2.32 ä). [10] The PÀP bonds to the tetracoordinate PX 2 phosphonium atom are shorter than those to the remaining naked P atoms by about 0.06 to 0.08 ä.…”

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

“…with cyclopentadienyl iron or iridium carbonyl species (Barr et al, 1991;Scheer et al, 1996), and in the tricyclic [3.3.0.0 3,7 ]octaphosphane (Butts et al, 2008). Huang and Diaconescu (2012).…”