Synthesis and characterization of (Et/sub 4/N)(M(CO)/sub 5/SR) and (Et/sub 4/N)/sub 2/(M/sub 2/(CO)/sub 8/(SR)/sub 2/) complexes (M = Cr, Mo, W). Ligand substitution reactions and x-ray crystal structure of (Et/sub 4/N)/sub 2/(W/sub 2/(CO)/sub 8/(SPh)/sub 2/)
A series of complexes (Et/sub 4/N)(M(CO)/sub 5/SR) (M = Cr, Mo, W; R = H, Ph), have been synthesized and characterized by /sup 1/H and /sup 13/C NMR and ir spectroscopies. Gentle heating causes these complexes to lose a carbonyl ligand, yielding the doubly bridged sulfur dimers M/sub 2/(CO)/sub 8/(..mu..-SR)/sub 2//sup 2 -/. The x-ray crystal structure of (Et/sub 4/N)/sub 2/(W/sub 2/(CO)/sub 8/(SPh)/sub 2/) has been determined. The complex crystallizes in the triclinic space group P /anti 1/ with unit cell parameters a = 9.8664 (17) /angstrom/, b = 9.8566 (22) /angstrom/, c = 11.8270 (26) /angstrom/, ..cap alpha.. = 65.790 (16)/degrees/, ..beta.. = 81.710 (16)/degrees/, ..gamma.. = 82.000 (16)/degrees/, V = 1034.0 (4) /angstrom//sup 3/, and Z = 1. Both mono- and dinuclear metal complexes readily react with phosphorus donor ligands to afford the carbon monoxide substituted complexes cis-M(CO)/sub 4/(P)(SR)/sup -/ (P = PMe/sub 3/, P(OMe)/sub 3/, PPh/sub 3/). In addition, the dimers react with 1 atm of carbon monoxide to re-form the mononuclear species M(CO)/sub 5/SR/sup -/ in quantitative yields. Unsuccessful attempts to insert CO/sub 2/, COS, or CS/sub 2/ into the M-SR bond in the M(CO)/sub 5/SR/sup -/ derivatives are noted. 25 references, 3 figures, 15 tables.
- Research Organization:
- Texas A and M Univ., College Station (USA)
- OSTI ID:
- 6181315
- Journal Information:
- Inorg. Chem.; (United States), Vol. 27:20
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AROMATICS
SYNTHESIS
CARBONYLS
CHROMIUM COMPLEXES
MOLYBDENUM COMPLEXES
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
TUNGSTEN COMPLEXES
CRYSTAL STRUCTURE
EXPERIMENTAL DATA
COMPLEXES
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation