The redox nature of the reaction of β-rhenium(IV) chloride with triphenylphosphine in acetonitrile, and the crystal structure of the reduction product trichloro(acetonitrile)bis(triphenylphosphine)rhenium(III)

Abstract

I d i a n a 47907)Summary An unusual redox reaction of P-rhenium(Iv) we studied its reactivity towards a variety of donor molechloride with triphenylphosphine in acetonitrile is cules using acidified methanol or acetone as reaction solvent. described, and the crystal structure of one of the reduc-Under these conditions, the reaction products were typical tion products, ReC1,,2PPh3,MeCN shows that this moleof those formed by the rhenium(II1) anion [RezC1,I-) ;2 in cule contains o-bonded acetonitrile.no instances did we isolate rhenium(1v) complexes of the type ReC1,,2L. We now find that by using strictly anhydrous conditions, the reactions of this halide are FOLLOWING our chance discovery of the new halide p-ReCl,,l

Preparation and structure of mer-trichloro(acetonitrile)bis-(triphenylphosphine)osmium(III)

“…Table 2. Bond distances and bond angles within the molecule are very similar to those observed in 0sC13(NH3)(P(C6H,)3)2 (1 I), r n e r -0~C l~( P ( C H~)~-(C6H5)), (16), and the Re analogue, ReC13(CH3-CN)(P(C,H,),), (14). The solid state deviations from octahedral geometry at the 0 s atom are most apparent in the displacement of Cl(2) and Cl(3) away from Cl(1) towards the CH3CN ligand, Cl(2)-0s-Cl(3) 17 1.04(7)".…”

“…It should be noted that no infrared band attributable to the nitrile stretching vibration of acetonitrile coordinated to osmium is observed in the region 2500-1800 cm-I in which such absorptions usually occur (12,13). The absence of a nitrile stretching band has been reported for a Re analogue (14) and other species containing N-bonded acetonitrile ligands (15).…”

“…1. The shortest intermolecular non-bonding contact is 2.32A between H atoms attached to phenyl C atoms C (14) and C(46). Intramolecular dimensions are given in Table 2; in this and all other tables estimated standard deviations are given in parentheses.…”

Synthesis and structural characterization of the novel unusual oxido-bridged rhenium complex with Re atoms in two different coordination environments

“…Based on experimental data (see Experimental section [20]) the following scheme for decomposition of the title complex on air may be proposed (the chlorine gas may be detected analogously as in the case of the complex formation): It is probable, that during this process the Re(IV) centre is reduced to Re(III) and concurrently Re(III) is oxidized by oxygen to Re(V). This corresponds to the studies carried out by Drew et al [36], who investigated reactions of [ReCl 3 (PPh 3 ) 2 (CH 3 CN)] complex with pyridine derivatives (L) and thus obtained [ReCl 3 L 2 (PPh 3 )] products, which on exposure to air underwent oxidation to salts containing a [ReO 2 (py) 4 ] + cation.…”

Rhenium Coordination Compounds: Analysis and Classification of Crystallographic and Structural Data

“…Of these, the first two are found in (7) 1781.5 (8) 1038.6(4) 1109.4 (4) Footnotes to Table 4 a. Distortion from perfect D Sh symmetry is evident in the bond angles as can be seen by comparing F(eq)-Re-F(eq) (70.3 (7) A capped octahedral geometry about the rhenium(III) is found in Re(CNtol) 4 Br 3 /117/ with three isocyanide (Re-C = 200.4 (8,19) pm) and three bromide (Re-Br = 261.72 (11,91) pm) ligands in a For the higher coordination numbers in Table 4 Table 4 it can be seen that they increase as the size and number of coordinated ligands increases. The -first number in brackets is the esd., the second is the maximum deviation -from the mean.…”