η⁵:η² Coordination of a cyclo‐E₅ Ligand, EP, As

Abstract

An unusual, additional side‐on coordination of an iridium center and a rhodium complex fragment with 16 valence electrons is realized in the new compounds 1. Compounds 1a, E = P, M = Ir, and 1b, E = As, M = Rh, were prepared from the sandwich complexes [Cp*Fe(η5‐E5)]. The isomers of 1a and 1b with terminal η1 coordination of the metal complex fragment have been obtained as well.

1-Triorganylstannyl-1,2,4-triphosphole: A Versatile Starting Material for Phosphorus-Rich Cage Compounds and π-Complexes

“…[30] On the other hand, in the case of cyclo-P n (n 5, 6) [43] or phosphorusrich P heterocycles as middle decks, [9,10] 34 VE are avoided and 26 to 30 VE are found; these compounds are also nonslipped. The only exceptions to these findings are the aforementioned compounds [(Cp*Fe(m,h 5 :h 2 -C 2 tBu 2 P 3 )RhCp*(CO)], [31] [(Cp*Fe(m,h 5 :h 2 -cyclo-P 5 )IrCp*(CO)], [32] and 11. Consequently, the reason for their pronounced slippage must be connected with the specific interaction between the phosphorus atoms of such P-rich ring ligands and transition metal atoms.…”

“…To the best of our knowledge, comparable m, [32] These two examples have the same total valence electron count as 11 of 34 and exhibit a P À P bond elongation of the same magnitude for the two phosphorus atoms that bridge the two metal atoms. On the other hand, they differ strongly from 11 in the electron distribution between the two halves of the dinuclear complexes, as they have been described as the addition products of the two closely related 16 VE complex fragments Cp*RhCO or Cp*IrCO to closed shell 18 VE oligophosphaferrocene derivatives.…”

Structures and Properties of Spherical 90‐Vertex Fullerene‐Like Nanoballs

“…All solvents were dried by standard procedures and distilled freshly prior to use. [Cp*FeA C H T U N G T R E N N U N G (h 5 -P 5 )], [33] 31 P MAS NMR spectra were recorded at 162.01 MHz on a Bruker DSX 400 solid-state NMR spectrometer equipped with a 2.5 mm high-speed spinning probe operated at 30 kHz spinning rate. Spectra were recorded by a rotor-synchronized Hahn spin echo sequence, generated with 908 pulse lengths of about 4 ms and a relaxation delay of 180 s. This delay was shown to be sufficient to produce quantitatively representative spectra.…”

Metal-Mediated Degradation and Reaggregation of White Phosphorus

“…Similarly, during the cothermolysis of 66 with [{Cp x Fe(CO) 2 99,100], diphosphorus ligands may be installed into a dodecahedron, while P 1 ligands may be incorporated in a distorted trigonal pyramid. The formation of these heterometal complexes through a synthetic procedure, which leaves out the use of white phosphorus, nicely illustrates the potentiality of P 5 complexes to serve as sources of phosphorus units.…”