Rhodium(I) Complexes of 1,2,5-Triphenylphosphole Oxide

Abstract

Rhodium trichloride hydrate and rhodium carbonyl chloride react with 1,2,5-triphenylphosphole oxide (TPPO) to produce a rhodium(I) complex [RhCl(TPPO)]2, where the metal is bonded to the ligand through the π system. This complex reacts with FeCl3 to produce RhCl(TPPO).FeCl3 where the iron is bonded through the oxygen of the P=O group. Reactions of [RhCl(TPPO)]2 with other species including nitrogen, phosphorus, and sulfur bases and carbon monoxide are described.

Rhodium(I) and (III) Complexes of Some Phospholes and Their Behavior as Homogeneous Hydrogenation Catalysts

“…The infrared spectrum of this complex in the 1100-1200 cm-' region shows that the TPPO is n-bonded to the rhodium (cj: ref. 2), and the complex is analogous to RhCI(TPPO)(Ph,P) which has been previouslv reported (2). That the rhodium has a strange; affinity towards the n-system of the TPPO in the presence of an excess of TPP again emphasizes the relatively poor donor properties (1) and probably aromatic nature of the substituted phosphole system.…”

“…RhC1,.3H20 in ethanol reacts with TPPS under reflux to give a brown solid which can be recrystallized from methylene chloride as RhCI(TPPS).CH,CI,. The phosphole sulfide, in contrast to TPPO (2), is believed to be bonded to the rhodium through the sulfur atom as shown by a shift in the P-S stretching frequency from 637 cm-' in the free ligand to either 625 or 595 cm-' in the complex. This difference in behavior of the metal towards the 0 and S donor atoms is not unexpected since rhodium falls into the "class b" acceptor category (9).…”

“…We have previously reported transition metal complexes of 1,2,5-triphenylphosphole (TPP) (a derivative of the aromatic phosphole system) and its oxide (TPPO), sulfide (TPPS), and selenide (1,2). Coordination of the ligands to the metal ions occurs through the donor atoms in all cases except for the TPPO complexes of Rh(1) where the n-diene system of the ligand is involved (2).…”

“…Coordination of the ligands to the metal ions occurs through the donor atoms in all cases except for the TPPO complexes of Rh(1) where the n-diene system of the ligand is involved (2). In view of the interesting complexes obtained from the rhodium system, a study of reactions between some other unsaturated cyclic phosphines and rhodium halides heated under reflux for at least 24 h, the stable, yellow-brown hydrido complex RhHC12 (TPP), is produced.…”

Synthesis, spectroscopic characterization, and magnetic properties of a mixed-valence copper(I,II) acetato complex with triphenylphosphine. Crystal structure of hexa-µ-acetato-tetrakis(triphenylphosphine)tetracopper(I,II)

“…The copper(r1) atoms are bonded together by four bridging acetate groups thus forming the dimeric Cu,( O,CMe), unit as in copper(r1) acetate monohydrate.' 5 * 1 6 Two molecules of triphenylphosphine and one acetate group are bonded to each copper(1) atom thus forming two molecular Cu(0,CMe)-(PPh,), ligands, which are bonded to the copper(1r) atoms in the Cu,(O,CMe), unit through the oxygen atoms O(1) and O( 1 ').…”