54873-11-9

Upstream product

• 20540-69-6 pentacarbonyl(methoxymethylcarbene)chromium⁽⁰⁾ 
• 1135-34-8 N-benzylideneaniline hydrochloride 
• 109283-12-7 lithium pentacarbonylchromate 
• 420-37-1 trimethoxonium tetrafluoroborate 
• 102-92-1 Cinnamoyl chloride 
• 4187-87-5 1-Phenyl-2-propyn-1-ol 
• 199620-14-9 chromium⁽⁰⁾ hexacarbonyl 

Downstream Products

• 960502-93-6 2-tributylstannyl-3,4-diphenylcyclopent-2-enone 
• 156124-52-6 (CO)5CrC₄H₈N₂ 

Relevant academic research and scientific papers

Activation of prop-2-yn-1-ols by metal carbonyls: Synthesis of (alkoxyalkenylcarbene)- and (aminoalkenylcarbene)chromium and -tungsten complexes

Fischer type methoxyalkenylcarbene complexes (CO)5M=C(OMe)(CH=CRR′) have been prepared in one step by photolysis of M(CO)6 [M = Cr, W] in tetrahydrofuran-methanol, in the presence of prop-2-yn-1-ol derivatives HC≡CC(OH)(R)(R′) [R, R′ = Me; R = H, R′ = Me, Ph, C6H4-p-NMe2]. Photolysis of a tetrahydrofuran-methanol solution of M(CO)6 with HC≡CC(OH)(H){(CH=CH)nCH=CRR′} [n = 0 R, R′ = Me; R = H, R′ = H, Me, Ph, C6H4-p-NMe2, C5H11; n = 1 R = H, R′ = Me] provides the new dienyl- and trienylcarbene complexes (CO)5W=C(OMe)(CH=CHCH=CRR′) and (CO)5M=C(OMe)(CH=CHCH=CHCH=CHMe) in 30-70% yields. Alkoxyalkenylcarbene complexes (CO)5M=C(OCH2Z)(CH=CRR′) are prepared analogously by using other primary alcohols ZCH2OH [Z = CH2CH(Me)(Et), CH2-CH2C≡CMe, CH2CH2CH=CH2, CH2CH2C(Me)=CH2. [(Alkenyloxy)alkenylcarbene]tungsten complexes undergo smooth thermal intramolecular cyclopropanation reactions leading to 1-alkenyl-2-oxabicyclo[3.1.0]hexane compounds. Finally, a series of aminodienylcarbene complexes (CO)5W=C(NHR′)(CH=CHCH=CHR) [R = Ph, C5H11; R′ = CHMe2, CMe3, CH2-CH=CH2, CH2CHMe2] have been synthesized by aminolysis of the corresponding methoxydienyl carbenes.

Preparation of acylpentacarbonylchromate salts and alkoxycarbene pentacarbonyl complexes of chromium employing the pentacarbonylchromate dianion ([Cr(CO)5]2-)

The in situ generated lithium and sodium salts of [Cr(CO)5]2- (3) react rapidly and cleanly with a variety of aryl and alkyl acid chlorides at -78°C in THF to provide solutions of the corresponding acylpentacarbonylchromate salts M′[RC(O)Cr(CO)5] (M′[1], M′ = Li, Na). Subsequent O-methylation of 1 produces Fischer-type alkoxycarbene complexes in yields competitive with established methodologies. This two-step procedure has enabled the preparation of arylmethoxycarbene complexes such as (CO)5Cr=C(OMe)-{2,5-(OAc)2C6H3} (2g) which are otherwise inaccessible by the standard Fischer synthesis. Alkoxycarbene complexes of molybdenum and tungsten may be prepared analogously from [Mo(CO)5]2- and [W(CO)5]2-.