Preparation and structure of a multiply bonded dirhenium(5+) species bridged by two diphosphinomethane ligands

Cotton, F. Albert; Shive, Larry W.; Stults, B. Ray

doi:10.1021/ic50163a049

Cited by 22 publications

(3 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is interesting to note that in the structure of the mixed-valence Re II Re III complex Re 2 Cl 5 (dppm) 2 , the Re-Re separation is 2.263(1) and the P-Re-Re-P torsion angle is 3.99Њ. 14 The torsion angle is lower, as expected, but the Re-Re distance is similar to other Re II Re II complexes listed in Table 3. This example underscores the danger in equating the Re-Re separation with formal bond order or oxidation state.…”

Section: Resultssupporting

confidence: 67%

Structural, electronic and magnetic properties of metal–metal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands

et al. 2003

View full text Add to dashboard Cite

The syntheses, spectroscopic properties, redox chemistry, and solid-state structures of products obtained from the reaction of Re 2 Cl 4 (dppm) 2 (dppm = bis(diphenylphosphino) methane) with the polycyano acceptors TCNQ (7,7,8,8tetracyanoquinodimethanido) and DM-DCNQI (2,5-dimethyl-N,NЈ-dicyanoquinonediimine) are described. The compounds [Re 2 Cl 4 (dppm) 2 ] 2 (µ-TCNQ), 1, and [Re 2 Cl 4 (dppm) 2 ] 2 (µ-DM-DCNQI), 2, have been prepared by reaction of two equivalents of Re 2 Cl 4 (dppm) 2 with TCNQ and DMDCNQI, respectively, in THF or CH 2 Cl 2 . A single-crystal X-ray crystallographic study of [Re 2 Cl 4 (dppm) 2 ] 2 (µ-TCNQ)ؒ10THF revealed the presence of a trans-µ 2 bidentate mode for the bridging TCNQ ligand that joins two Re 2 Cl 4 (dppm) 2 molecules through equatorial positions. In a similar fashion, the compound [Re 2 Cl 4 (dppm) 2 ] 2 (µ-DM-DCNQI)ؒ10THF consists of two Re 2 units coordinated to the two nitrile positions of the DM-DCNQI ligand. The electronic properties of both compounds are unusual in that they exhibit intense, broad absorptions that span the near-IR region and extend into the mid-IR. The electrochemistry of the compounds consists of numerous oxidation and reduction processes in the range of ϩ2.0 to Ϫ2.0 V as determined by cyclic voltammetry. Both 1 and 2 exhibit temperature independent paramagnetism (TIP) with large χ TIP values of 7.29 × 10 Ϫ3 and 6.23 × 10 Ϫ3 emu mol Ϫ1 , respectively.

show abstract

Section: Resultssupporting

confidence: 67%

Structural, electronic and magnetic properties of metal–metal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands

et al. 2003

View full text Add to dashboard Cite

show abstract

“…The tendency of halide ions to stabilise higher valent complexes more commonly results in the scavenging of halide upon oxidation, often at the expense of neutral donor ligands. 3,14,15 In the present case there is no evidence to suggest expulsion of isocyanide, since free isocyanide would be readily detected in the IR spectroelectrochemical experiments on account of the very strong ν CN band for free CNBu t , which occurs at 2139 cm Ϫ1 .…”

contrasting

confidence: 51%

Oxidative and reductive activation of tetra-n-butylammonium trans-tetrabromobis(tert-butylisocyanide)ruthenium( III): a spectroelectrochemical study

Dulaimi¹,

Clark²,

Humphrey³

1997

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

show abstract

“…The Re−Cl ax distances in 3 (Table ) are comparable to those in other dirhenium complexes having axial chlorides, e.g., Re 2 Cl 5 (dppm) 2 (2.575 Å), Re 2 Cl 5 (NO)(dmpm) 2 (2.621 Å), and Re 2 (DMF) 4 Cl 2 (2.527 Å) . The rest of the metal−ligand bond lengths in [Re 2 Cl 7 (bdppp)] - are very similar to the corresponding distances in 2 .…”

Section: Resultssupporting

confidence: 65%

Ligand Exchange or Reduction at Multiply Bonded Dimetal Units of Molybdenum and Rhenium by 2,6-Bis(diphenylphosphino)pyridine

et al. 1998

View full text Add to dashboard Cite

Reaction of 2,6-bis(diphenylphosphino)pyridine (bdppp or (Ph(2)P)(2)Py)) with K(4)Mo(2)Cl(8) in refluxing methanol gives Mo(2)Cl(4)(bdppp)(2) (1) with retention of the quadruple Mo-Mo bond. However, the quadruply bonded octachlorodirhenate(III) anion, Re(2)Cl(8)(2)(-), reacts with bdppp under similar conditions to afford Re(2)Cl(4)(bdppp)(2) (2), which has a triply bonded dirhenium(II) core, Re(2)(4+). An intermediate species, [Bu(n)(4)N][Re(2)Cl(7)(bdppp)] (3), containing an Re(2)(6+) core and only one bridging bdppp ligand has also been isolated. The crystal structures of complexes 1-3 have been investigated by X-ray crystallography. In all cases the potentially tridentate bdppp acts as a bidentate ligand using one N and one of the P atoms, leaving the second phosphorus atom noncoordinated. The crystallographic parameters for these structures are as follows: Mo(2)Cl(4)(bdppp)(2).2CH(2)Cl(2) (1.2CH(2)Cl(2)), monoclinic space group P2(1)/c with a = 15.475(2) Å, b = 11.5958(7) Å, c = 16.7637 (6) Å, beta = 98.178(5) degrees, Z = 2; Re(2)Cl(4)(bdppp)(2) (2), monoclinic space group P2(1)/n with a = 16.173(2) Å, b = 11.285(1) Å, c = 28.771 (4) Å, beta = 96.17(1) degrees, Z = 4; [Bu(n)(4)N][Re(2)Cl(7)(bdppp)].CH(2)Cl(2) (3.CH(2)Cl(2)), triclinic space group P&onemacr; with a = 16.054(2) Å, b = 18.562(3) Å, c = 20.205 (6) Å, alpha = 89.71(2) degrees, beta = 73.21(1) degrees, gamma = 73.47(2) degrees, Z = 4.

show abstract

Preparation and structure of a multiply bonded dirhenium(5+) species bridged by two diphosphinomethane ligands

Cited by 22 publications

References 30 publications

Structural, electronic and magnetic properties of metal–metal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands

Structural, electronic and magnetic properties of metal–metal bonded dinuclear rhenium complexes bridged by organocyanide acceptor ligands

Oxidative and reductive activation of tetra-n-butylammonium trans-tetrabromobis(tert-butylisocyanide)ruthenium( III): a spectroelectrochemical study

Ligand Exchange or Reduction at Multiply Bonded Dimetal Units of Molybdenum and Rhenium by 2,6-Bis(diphenylphosphino)pyridine

Contact Info

Product

Resources

About