Synthesis and characterization by sup 1 H, sup 13 C, and sup 19 F NMR spectroscopy of (CH sub 3 CN) sub n (CO) sub 4 minus n (NO)W(. mu. -F)BF sub 3 and ((CH sub 3 CN) sub n+1 (CO) sub 4 minus n (NO)W)(BF sub 4 )(n = 0 minus 2), tungsten mononitrosyl carbonyl cations with labile acetonitrile and ((. mu. -F)BF sub 3 ) sup minus ligands
- Univ. of California, Los Angeles (USA)
Addition of (NO)(BF{sub 4}) to CH{sub 3}CNW(CO){sub 5} in CH{sub 2}Cl{sub 2} gives a mixture of five mononitrosyl compounds, mer-(cis-CH{sub 3}CN)(trans-NO)(CO){sub 3}W({mu}-F)BF{sub 3} (1), (mer,cis-(CH{sub 3}CN){sub 2}W(CO){sub 3}(NO))(BF{sub 4}) (2a), cis,cis,trans-(CH{sub 3}CN){sub 2}(CO){sub 2}(NO)W({mu}-F)BF{sub 3} (3), (fac-(CH{sub 3}CN){sub 3} W(CO){sub 2}(NO))(BF){sub 4} (4a), and trans-(NO)(CO){sub 4}W({mu}-F)BF{sub 3} (5); in a typical experiment the yield is 90%, and the ratio 1:2a:3:4a:5 is 47:14:11:1:27. Support for the identities of 1-5 is obtained by reaction of the mixture with Me{sub 3}P, giving (mer-(cis-CH{sub 3}CN)(trans-Me{sub 3}P)W(CO){sub 3}(NO))(BF{sub 4}) (7a), (cis,cis,trans-(CH{sub 3}CN){sub 2}(CO){sub 2}(NO)W(PMe{sub 3}))(BF{sub 4}) (8a), (trans-Me{sub 3}P(CO){sub 4}WNO)(BF{sub 4}) (9), and the previously reported compound (mer,cis-(Me{sub 3}P){sub 2}W(CO){sub 3}(NO))(BF{sub 4}) (10a). The reaction mixtures are analyzed by IR and {sup 1}H, {sup 13}C, and {sup 19}F NMR spectroscopy. In particular, the {sup 13}C NMR spectrum exhibits quintets for the carbonyl ligands of 1,3, 5 due to a dynamic spinning process of the (({mu}-F)BF{sub 3}){sup {minus}} ligand, and the {sup 19}F NMR spectrum exhibits doublets for the terminal fluorine atoms (which are further separated into {sup 10}B and {sup 11}B isotopomers) near {minus}153 ppM and quartets for the bridging fluorine atoms from {minus}203 to {minus}238 ppM. Independent synthesis and isolation in good yield of 2b-c, 4a-d, 7b-c, and 8b (where the anions for a-d are (BF{sub 4}){sup {minus}}, (SbF{sub 6}){sup {minus}}, ((C{sub 6}H{sub 5}){sub 4}B){sup {minus}}, and (PF{sub 6}){sup {minus}}{sup {minus}}, respectively) are described, as are the independent synthesis and spectroscopic characterization of 3, 5, and 6. 4 figs., 1 tab.
- OSTI ID:
- 7121450
- Journal Information:
- Inorganic Chemistry; (USA), Vol. 29:4; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BORON COMPOUNDS
CHEMICAL PREPARATION
CARBONYLS
FLUORINE COMPOUNDS
NITROSO COMPOUNDS
TUNGSTEN COMPLEXES
ACETONITRILE
CARBON 13
EXPERIMENTAL DATA
FLUORINE 19
NMR SPECTRA
PROTONS
BARYONS
CARBON ISOTOPES
COMPLEXES
DATA
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
FERMIONS
FLUORINE ISOTOPES
HADRONS
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NITRILES
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation