Preparation of some dithiocarbene complexes, W(CO)/sub 5/(C(SR)/sub 2/), and their reactions with nucleophiles
The reaction of W(CO)/sub 5/CS with /sup -/SR (R = CH/sub 3/, C/sub 2/H/sub 5/, i-C/sub 3/H/sub 7/, n-C/sub 4/H/sub 9/, or t-C/sub 4/H/sub 9/) followed by alkylation of the resulting dithioester anion, W(CO)/sub 5/(C(==S)SR)/sup -/, by R'I(R' = CH/sub 3/ or C/sub 2/H/sub 5/) produces (bis(alkylthio)carbene)tungsten complexes, W(CO)/sub 5/(C(SR)(SR')), in good yield. The substituted tetracarbonyl(bis(methylthio)carbene)tungsten complexes cis-W-(CO)/sub 4/(P(OCH/sub 3/)/sub 3/)(C(SCH/sub 3/)/sub 2/) and cis-W(CO)/sub 4/(P(OPh)/sub 3/)(C(SCH/sub 3/)/sub 2/) are prepared by an analogous route using cis-W-(CO)/sub 4/L(CS), where L = P(OCH/sub 3/)/sub 3/ or P(OPh)/sub 3/. (Cyclic dithiocarbene)tungsten complexes may be prepared in a similar manner from W(CO)/sub 5/CS, NaS(CH/sub 2/)/sub n/SH (n = 2, 3, 4), and CH/sub 3/I to give W(CO)/sub 5/CS(CH/sub 2/)/sub n/S. The carbene complex W(CO)/sub 5/(SCH/sub 3/)(SFe(CO)/sub 2/Cp)) (Cp = eta/sup 5/C/sub 5/H/sub 5/) is prepared by the reaction of W(CO)/sub 5/(C(==S)(SCH/sub 3/))/sup -/ with CpFe-(CO)/sub 2/(THF)/sup +/. Isocyanide complexes, W(CO)/sub 5/CN-R, are formed when W(CO)/sub 5/(C(SCH/sub 3/)/sub 2/) reacts with primary amines, RNH/sub 2/, where R = CH/sub 3/, (CH/sub 2/)/sub 2/CH/sub 3/, CH/sub 2/Ph, C/sub 6/H/sub 11/, and (CH/sub 2/)/sub 2/N(CH/sub 3/)/sub 2/, or the diamine NH/sub 2/(CH/sub 2/)/sub 3/NH/sub 2/. When cis-W(CO)/sub 4/(P(OPh)/sub 3/)(C(SCH/sub 3/)/sub 2/) is reacted with NH/sub 2/CH/sub 2/Ph and NH/sub 2/(CH/sub 2/)/sub 3/NH/sub 2/, isocyanide complexes are also formed. The reaction of W(CO)/sub 5/(C(SCH/sub 3/)/sub 2/) with secondary amines NH(CH/sub 3/)/sub 2/, HN(CH/sub 2/)/sub 2/OCH/sub 2/CH/sub 2/, or HN(CH/sub 2/)/sub 4/CH/sub 2/ yields (aminothiocarbene)tungsten complexes, W(CO)/sub 5/(C(SCH/sub 3/)NR/sub 2/). The compound (N(C/sub 2/H/sub 5/)/sub 4//sup +/)(W(CO)/sub 5/CN/sup -/) was formed from the reaction of W(CO)/sub 5/(C(SCH/sub 3/)/sub 2/) with (N(C/sub 2/H/sub 5/)/sub 4//sup +/)(N/sub 3//sup -/).
- Research Organization:
- Ames Lab., IA
- DOE Contract Number:
- W-7405-ENG-82; WPAS-KC-03-02-01
- OSTI ID:
- 6041026
- Journal Information:
- Inorg. Chem.; (United States), Vol. 20:9
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMINES
CHEMICAL REACTIONS
TUNGSTEN COMPLEXES
SYNTHESIS
ALKYLATION
CARBONYLS
INFRARED SPECTRA
NMR SPECTRA
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
COMPLEXES
ORGANIC COMPOUNDS
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)