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

Journal Article · Wed Feb 21 04:00:00 EST 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00329a029· OSTI ID:7121450

Hersh, W H ^[1]

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1. 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), Journal Name: Inorganic Chemistry; (USA) Vol. 29:4; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ACETONITRILE
BARYONS
BORON COMPOUNDS
CARBON 13
CARBON ISOTOPES
CARBONYLS
CHEMICAL PREPARATION
COMPLEXES
DATA
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FERMIONS
FLUORINE 19
FLUORINE COMPOUNDS
FLUORINE ISOTOPES
HADRONS
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NITRILES
NITROSO COMPOUNDS
NMR SPECTRA
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PROTONS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES