Structural characterization of the triply bonded dirhenium(II) complexes Re/sub 2/Cl/sub 4/(. mu. -Ph/sub 2/PCH/sub 2/PPh/sub 2/)/sub 2/ and. cap alpha. -Re/sub 2/Cl/sub 4/(Me/sub 2/P(CH/sub 2/)/sub 2/PMe/sub 2/)
The complexes Re/sub 2/Cl/sub 4/(LL)/sub 2/, where LL are the bidentate ligands Ph/sub 2/PCH/sub 2/PPh/sub 2/ (dppm) (1) and Me/sub 2/P(CH/sub 2/)/sub 2/PMe/sub 2/ (dmpe) (2), which both possess the electronic configuration sigma/sup 2/..pi../sup 4/-delta*/sup 2/-delta/sup 2/ and thus formally a metal-metal triple bond, have been structurally characterized by X-ray crystallography. Re/sub 2/Cl/sub 4/(dppm)/sub 2/ (1): Re/sub 2/Cl/sub 4/P/sub 4/C/sub 50/H/sub 44/; monoclinic, P2/sub 1//n; a = 11.647 (3) A, b = 12.849 (4) A, c = 38.691 (9) A, ..beta.. = 85.96 (2)/sup 0/, V = 5776 (43) A/sup 3/, Z = 4. The molecule has two dppm molecules spanning the Re-Re bond. The two fused five-membered rings assume twist-boat conformations, leading to a completely staggered arrangement of the substituents on the two rhenium atoms. The average Cl-Re-Re-Cl torsion angle is 56 (1)/sup 0/, and the Re-Re bond length is 2.234 (3) A. Re/sub 2/Cl/sub 4/(dmpe)/sub 2/ x CH/sub 3/OH (2) was isolated and crystallized as the ..cap alpha.. isomer, viz., with the dmpe ligands chelating. The crystallographic parameters are as follows: Re/sub 2/Cl/sub 4/P/sub 4/OC/sub 13/H/sub 36/; orthorhombic, Ccma (nonstandard setting of Cmca); a = 11.595 (2) A, b = 14.475 (2) A, c = 14.925 (2) A, V = 2505 (1) A, Z = 4. The dimetallic unit has a Re-Re bond length of 2.264 (1) A and an eclipsed conformation with the geminal chlorides in a cis configuration. The five-membered chelate rings have envelope conformations. 16 references, 4 figures, 2 tables.
- Research Organization:
- Texas A and M Univ., College Station
- OSTI ID:
- 6040455
- Journal Information:
- Inorg. Chem.; (United States), Vol. 24:16
- Country of Publication:
- United States
- Language:
- English
Similar Records
Kinetics and mechanism of molecular A-frame formation. Reactions of cyclo-octasulfur and sulfur dioxide with Pt/sub 2/Cl/sub 2/(. mu. -Ph/sub 2/PCH/sub 2/PPh/sub 2/)/sub 2/ and related binuclear platinum complexes
Chemistry in environmentally benign media. 3. Synthesis and characterization of rhenium(V) complexes derived from novel water-soluble (hydroxymethyl)phosphines. Crystal structures of [Re(O){sub 2}[(HOH{sub 2}C){sub 2}PC{sub 6}H{sub 4}P(CH{sub 2}OH){sub 2}]{sub 2}]I and [Re(O){sub 2}[(HOH{sub 2}C){sub 2}PCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 2}]{sub 2}]Cl
Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHLORIDES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
ELECTRONIC STRUCTURE
ORGANIC COMPOUNDS
PHOSPHORUS COMPLEXES
RHENIUM COMPLEXES
BOND ANGLE
BOND LENGTHS
CHEMICAL BONDS
DIMERS
EXPERIMENTAL DATA
LATTICE PARAMETERS
LIGANDS
SPACE GROUPS
X-RAY DIFFRACTION
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMENSIONS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
LENGTH
NUMERICAL DATA
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
360602* - Other Materials- Structure & Phase Studies
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)