Reactions of Rhenium(V) Oxo and Nitrido Complexes with 1-Phenyl-2-(diphenylphosphino)ethanone (P⌒OH). Synthesis and Crystal Structure of ReOCl(P⌒O)₂and ReN(PPh₃)(P⌒O)₂

Abstract

Structurally related six-coordinated oxo ReOCl(P⌒O)2 and nitrido ReN(PPh3)(P⌒O)2 complexes were synthesized. The bidentate P⌒O- ligand forms oxo ReOCl(P⌒O)2 and nitrido ReN(PPh3)(P⌒O)2 complexes containing quasi-isostructural ReO(P⌒O)2 and ReN(P⌒O)2 units. The Cl site in the oxo compound is occupied by PPh3 in the nitride. PPh3 is smoothly displaced in solution by pyridine, 1-methylimidazole, and P(p-tolyl)3 with retention of stereochemistry.

Structures of a Tetradentate Ferrocenyl Ligand and Its Oxorhenium(V) Complex in Solution and in the Solid State

“…The RedO (Re-O(3)) bond length of 1.714(5) Å is longer than the bond lengths observed for similar six-coordinate Re(V) complexes, where bond lengths of 1.68-1.69 Å were found, 17b,35 except for the complexes [ReO(N 3 O 2 )]‚MeOH (N 3 O 2 ) N,N′-bis(salicylideneiminato)pentylene-1,5-diamine) 17b, 35 and [ReO(salphos)Cl 2 ] 36 in which the RedO bonds are 1.72(1) and 1.71(1) Å, respectively. The Re-O(1) and Re-O(2) bond lengths of 1.922(6) and 1.926(6) Å are within, but on the shorter side of, the expected range for Re-O bond lengths.…”

“…Distances of between 1.92 and 2.14 Å for Re-O single bonds cis with respect to the RedO bond and 1.92-2.09 Å for bonds trans to the RedO bond are documented. 35,36 The Re-N(1) bond length of 2.177(6) Å is much shorter than the Re-N(2) bond length of 2.292(6) Å. This is expected because the phosphorus atom trans to the N(1) atom, unlike the N(2) atom that is trans to an …”

Synthesis and spectroscopic investigation of the pyrazole complexes. The X-ray structure of [ReOBr 3 (OAsPh 3 )(pzH)]

“…The oxocomplexes are catalysts for organic reactions, models for active sites in heterogeneous processes and very useful starting reagents in the coordination chemistry [1][2][3][4][5].…”

“…In this paper we report the synthesis and spectroscopic investigation of [ReOX 3 (OAsPh 3 )(pzH)] complexes, obtained in the direct reactions of [ReOX 3 (OAsPh 3 )(AsPh 3 )] with pyrazole. The crystal structure of the pyrazole complex [ReOBr 3 (OAsPh 3 )(AsPh 3 )] was determined.…”

The Molecular and Electronic Structure of [ReOX3(AsPh3)(OAsPh3)] Complexes (X = Cl, Br)

“…Oxo-complexes are catalysts for organic reactions, models for active sites in heterogeneous processes and very useful starting reagents in coordination chemistry [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. They also appear to be involved in the catalytic cycles of a variety of metalloenzymes, for instance those of cytochrome P-450, nitrogenase and xanthine oxidase [15][16][17].…”