Poly(tertiary phosphines and arsines). 20. Some reactions of (methylamino)bis(dimethoxyphosphine) and crystal structure of (. mu. -carbonyl)(. mu. -(methylamino)bis(dimethoxyphosphine))bis(tricarbonyliron), CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/Fe/sub 2/(CO)/sub 7/
- Oak Ridge National Lab., TN
Reactions of the complexes (norbornadiene)M(CO)/sub 4/ (M = Cr and Mo) with CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/ give the corresponding CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/M(CO)/sub 4/ chelate complexes. Reactions of iron carbonyls with CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/ under appropriate conditions give the bridged binuclear complexes )CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/)/sub n/Fe/sub 2/(CO)/sub 9-2n/ (n = 1 and 2). The infrared v(CO) frequencies of metal carbonyl complexes of CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/ are consistently lower than those of analogous CH/sub 3/N(PF/sub 2/)/sub 2/ complexes, in accord with the lower ..pi..-acceptor strength of CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/ relative to that of CH/sub 3/N(PF/sub 2/)/sub 2/. Single-crystal X-ray diffraction analysis shows the complex CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/Fe/sub 2/(CO)/sub 7/ (3) to have an Fe-Fe bond 2.6606 (5) angstrom long that is bridged by one CO group and by the bidentate ligand CH/sub 3/N(P(OCH/sub 3/)/sub 2/)/sub 2/.The CO group, the N atom, and the midpoint of the Fe-Fe bond are located on a crystallographic mirror plane. The Fe-P bond length is 2.1919 (5) angstrom, and the P-N bond length is 1.665 (1) angstrom. The Fe/sub 2/P/sub 2/N ring conformation is almost exactly plane, unusual for either M/sub 2/P/sub 2/N or M/sub 2/P/sub 2/C rings. The Fe/sub 2/P/sub 2/N best plane is at approx. 90/sup 0/ to the best plane through the two Fe atoms and five of the carbonyl carbon atoms, including the bridging carbon. Except for the nearly plane Fe/sub 2/P/sub 2/N ring, the structure of the moiety Fe/sub 2/P/sub 2/N(CO)/sub 7/ is remarkably close, even in some rather fine details, to that of the moiety Fe/sub 2/P/sub 2/C(CO)/sub 7/ in CH/sub 2/(P(C/sub 6/H/sub 5/)/sub 2/)/sub 2/Fe/sub 2/(CO)/sub 7/ as described by Cotton and Troup.
- DOE Contract Number:
- W-7405-ENG-26
- OSTI ID:
- 6234734
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:10; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Metal complexes of fluorophosphines. 13. Reaction of fac-(CH/sub 3/CN)/sub 3/Mo(CO)/sub 3/ with (methylamino)bis(difluorophosphine). X-ray crystal structure analysis of a novel binuclear molybdenum fluorophosphine carbonyl complex with a bridging chlorine atom: (CO)/sub 2/Mo(/sup +/-CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 2/(. mu. -PF/sub 2/)(. mu. -Cl)Mo(CO)(PF/sub 2/NHCH/sub 3/)
Cyclopropenylidene approach to tricarbide complexes: Synthesis and structure of [M(CO){sub 5}(mu{sub 2}-C{sub 3}(OCH{sub 2}CH{sub 3} ))Fe(CO){sub 2}(Cp)] (M = Cr, Mo, W)
Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
BOND ANGLE
BOND LENGTHS
CARBONYLS
CHROMIUM COMPLEXES
COMPLEXES
CYCLOALKENES
DIMENSIONS
HYDROCARBONS
INFRARED SPECTRA
IRON COMPLEXES
LENGTH
MOLYBDENUM COMPLEXES
NORBORNADIENE
ORGANIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES