78234-36-3

Usage

Reaction

A well-defined tungsten-based alkyne metathesis catalyst first prepared by Professor Richard Schrock. The catalyst has been used to prepare a variety of products through alkyne metathesis, including natural products that contain large rings. Catalyst for alkyne metathesis.

Upstream product

• 15038-41-2 pentacarbonyl(tetrahydrofuran)chromium⁽⁰⁾ 
• 57125-20-9 ditungsten hexa-tert-butoxide 
• 78129-68-7 2,2-dimethylpropylidynephosphine 
• 36477-75-5 tungsten pentacarbonyl tetrahydrofuran 
• 240807-49-2 (η(5)-1,3-(t)Bu2C5H3)Mn(CO)2(THF) 

Downstream Products

• 82228-87-3 W(CPh)(OCMe₃)3 
• 98268-63-4 W(CHC(CH₃)3)(OC(CH₃)3)2(O₂CC₆H₅)2 
• 98268-60-1 W(CHC(CH₃)3)(OC(CH₃)3)2(OC₆H₅)2 
• 98268-62-3 W(CHC(CH₃)3)(OC(CH₃)3)2(OC₆F₅)2 
• 1122101-19-2 [(Me₃CC)W(1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato)(O-t-Bu)2] 
• 1071-81-4 2,2,5,5-tetramethylhexane 
• 22808-06-6 2,2,5,5-tetramethyl-3-hexene 
• 17530-24-4 di-tert-butylacetylene 
• 463-82-1 2,2-dimethylpropane 
• 75-84-3 2,2-dimethyl-propanol-1 
• 630-19-3 pivalaldehyde 
• 75-65-0 tert-butyl alcohol 
• 129960-82-3 (C₆H₅CH₂)3WCC(CH₃)3 

Relevant academic research and scientific papers

An approach to novel complexes with a tungsten-phosphorus triple bond

The metathesis reaction of [W2(OtBu)6] with tBuC≡P leads to the phosphide complex [(tBuO)3W≡P] (1), which can be stabilized when the reaction is carried out in the presence of Lewis acidic carbonyl complexes of the type [M(CO)5thf] (M = Cr, W). However, further reaction of the metathesis products [(tBuO)3W≡CtBu] and [(tBuO)3W≡P→M(CO)5] [M = W (4a), Cr (4b)] with tBuC≡P leads after subsequent 1,3-OtBu shift to the metallaphosphacyclobutadiene derivatives [(tBuO)2W{C(tBu)}2P(OtBu)] (2a) and [(tBuO)2WC(tBu)P{M(CO)5}-P(OtBu)] [M = W (5a), M = Cr (5b)]. To prevent the latter, the bulky phosphaalkyne Ar′C≡ P (Ar′ = 2,4,6-tBu3C6H2) was employed in the three-component reaction instead of tBuC≡ P. Surprisingly here, a head-to-tail dimerization of Ar′C≡P occurs to give the novel phosphinidene complexes [M(CO)4P(R′)C(Ar′)P{MCO)5}] [M = Cr (6a), M = W (6b); R′ = 2,4-tBu2-7-Me2-indanyl]. In the case of [W(CO)5thf], additionally, the complex [W(CO)2{(η2-PCAr′)W(CO)5} 2] (7) is formed. The function of [W2(OtBu)6] in this reaction is uncertain, but stoichiometric amounts of [W2(OtBu)6] are essential to obtain complex 6. Reduction of the size of the alkoxide ligands by the use of [W2(ONp)6] (Np = CH2tBu) in the three-component reaction with Ar′C≡P leads to the trinuclear cluster compounds [W3〈(μ3-P)-{W(CO) 5}〉(μ-ONp)3(ONp)6] (8) and [W3(μ3-P)(μ-ONp)3(ONp)6] (9). The crucial step of the side-product free synthesis of the phosphido complexes 4 is the introduction of MesC≡P (Mes = 2,4,6-Me3C6H2) into the three-component system of [W2(OtBu)6], RC≡P, and [W(CO)5thf]. Comprehensive structural and spectroscopic data are given for the products. Furthermore, a 31P NMR experiment was conducted following the reaction of [W2(OtBu)6] with MesC≡P from -70°C to ambient temperature. In the range of -60 to -40°C, a singlet at 845 ppm with one pair of tungsten satellites (1JW,P = 176 Hz) was observed for the complex [(tBuO)3W≡ P] (1).

Is it Possible to stabilise Complexes with a Tungsten-Phosphorus Triple Bond?

4-(But2C2P2)W(CO)5>2-(ButCP)W(CO)5>> 1 is prepared by treatment of ButCP with ; the reaction of t)6> with ButCP in the presence of (M = Cr, W) affords novel compounds of the type tO)3WP -> M(CO)5> (M = Cr, W), the first examples of a formal WP containing complex.