Related Experiment Video

Updated: Oct 2, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos^Ph Complexes

Published on: April 10, 2015

Mixed Chloride/Phosphine Complexes of the Dirhenium Core. 3. Novel Structures with Diethylphosphido-bridges and

F. Albert Cotton¹, Evgeny V. Dikarev, Marina A. Petrukhina

¹Laboratory for Molecular Structure and Bonding, P.O. Box 300012, Department of Chemistry, Texas A&M University, College Station, Texas 77842-3012.

Inorganic Chemistry

|October 24, 2001

Abstract:

The interaction between octachlorodirhenium anions and diethylphosphine has been shown to strongly depend on reaction conditions, mainly the nature of the solvent and the amount of phosphine. As a result, novel dirhenium products with oxidation states ranging from Re(II) to Re(IV) have been obtained. The reaction of [Re(2)Cl(8)](2)(-) with an excess of PEt(2)H in dichloromethane or acetonitrile led to the first example of a face-sharing complex of rhenium(IV) with three phosphido-bridges, namely [Bu(n)(4)N][Re(2)(&mgr;-PEt(2))(3)Cl(6)] (1). The unusual edge-sharing Re(2)(&mgr;-PEt(2))(2)Cl(4)(PEt(2)H)(4) (2) complex of rhenium(III) with C(i)() core symmetry, containing both terminal phosphines and phosphido-bridges, has been obtained by carrying out the reaction with an excess of PEt(2)H in a benzene (or propanol) - HCl mixture at room temperature. A new example of the 1,2,7,8-type of dirhenium(II) complex, Re(2)Cl(4)(PEt(2)H)(4) (3), having diethylphosphine ligands located cis on each Re atom, has been isolated from the reaction of [Re(2)Cl(8)](2)(-) with PEt(2)H in an ethanol-HCl medium. The solid-state structures of complexes 1-3 have been investigated by X-ray crystallography. Complexes 1 and 2 both crystallized in two forms: [Bu(n)(4)N][Re(2)(&mgr;-PEt(2))(3)Cl(6)] 1a, P2(1)/n with a = 10.482(1) Å, b = 16.512(2) Å, c = 23.986(2) Å, beta = 93.637(8) degrees, and Z = 4; [Bu(n)(4)N][Re(2)(&mgr;-PEt(2))(3)Cl(6)].1.5 C(7)H(8) 1b, C2/c with a = 38.746(9) Å, b = 10.322(2) Å, c = 27.277(3) Å, beta = 110.35(1) degrees, and Z = 8; Re(2)(&mgr;-PEt(2))(2)Cl(4)(PEt(2)H)(4) 2a, P2(1)/n with a = 11.081(3) Å, b = 11.029(3) Å, c = 15.627(2) Å, beta = 90.05(1) degrees, and Z = 2; 2b, P2(1)/c with a = 16.094(3) Å, b = 15.193(3) Å, c = 15.548(3) Å, beta = 100.98(3) degrees, and Z = 4. X-ray data for complex Re(2)Cl(4)(PEt(2)H)(4) 3 are as follows: P2(1)/n with a = 10.445(2) Å, b = 10.113(3) Å, c = 13.473(2) Å, beta = 102.17(2) degrees, and Z = 2. Three bridging &mgr;-PEt(2) groups in the face-sharing complex 1 span a short metal-metal distance of 2.4060(6) Å, averaged over 1a and 1b, with a small Re-PEt(2)-Re angle of 61.34(7) degrees. The rhenium-rhenium bond length in the edge-sharing complex 2 is 2.7545(7) Å, averaged over 2a and 2b, while the bridging Re-PEt(2)-Re angle is 72.16(6) degrees, and the P-Re-P angle for the terminal phosphine ligands is 87.11(7) degrees. The Re-Re bond distance in 3, 2.2533(8) Å, is typical for triply bonded dirhenium complexes, and the P-Re-P angle for the cis phosphine groups is 93.12(6) degrees.

More Related Videos

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)

Published on: November 22, 2016

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Related Concept Videos

Predicting Molecular Geometry

Predicting Molecular Geometry

VSEPR Theory for Determination of Electron Pair Geometries

Hybridization of Atomic Orbitals I

Hybridization of Atomic Orbitals I

The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...

Hybridization of Atomic Orbitals II

Hybridization of Atomic Orbitals II

sp3d and sp3d 2 Hybridization

Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

Chirality at Nitrogen, Phosphorus, and Sulfur

Chirality at Nitrogen, Phosphorus, and Sulfur

Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...

Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene

Electrophilic 1,2- and 1,4-Addition of X₂ to 1,3-Butadiene

Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.

Articles linked to this work by shared authors, journal, and citation graph.

Mixed Chloride/Amine Complexes of Dimolybdenum(II,II). 2. Reactions of Mo(2)Cl(4)(NHEt(2))(4) with Monodentate and Bidentate Phosphines. New Type of Compounds Mo(2)Cl(4)(diphosphine)(4).

Inorganic chemistry·2001

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

Inorganic chemistry·2001

Linear Tricobalt Compounds with Di-(2-pyridyl)amide (dpa) Ligands: Studies of the Paramagnetic Compound Co(3)(dpa)(4)Cl(2) in Solution.

Inorganic chemistry·2001

Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory.

Inorganic chemistry·2001

Mixed Chloride/Amine Complexes of Dimolybdenum(II,II). 4. Rotational Isomers of Mo(2)Cl(4)(R-py)(4) (R-py = 4-Picoline, 3,5-Lutidine, and 4-tert-Butylpyridine).

Inorganic chemistry·2001

Studies of Dirhodium Tetra(trifluoroacetate). 3. Solid State Isomers of the Compound Rh(2)(O(2)CCF(3))(4)(THF) Prepared by Sublimation.

Inorganic chemistry·2001

See all related articles