68433-34-1

Upstream product

• 16972-33-1 pentacarbonylhydridomanganese 
• 100-52-7 benzaldehyde 
• 68433-31-8 (C₆H₅)3PNP(C₆H₅)3⁽¹⁺⁾*(CO)4MnCOCH(C₆H₅)OCO^(1-)=(C₆H₅)3PNP(C₆H₅)3(CO)4MnCOCH(C₆H₅)OCO 

Downstream Products

• 68433-36-3 (C₄H₉)4N⁽¹⁺⁾*Mn(CO)5^(1-)=[(C₄H₉)4N][Mn(CO)5] 
• 100-52-7 benzaldehyde 
• 16972-33-1 pentacarbonylhydridomanganese 
• 68433-32-9 (CO)5MnCOCH(C₆H₅)OSi(CH₃)3 
• 10170-69-1 dimanganese decacarbonyl 
• 35479-44-8 1,2-bis(trimethylsiloxy)-1,2-diphenylethane 

Relevant academic research and scientific papers

Reactions of (CO)5MnSi(CH3)3 with organic carbonyl compounds

Reactions of (CO)5MnSi(CH3)3 (1) with organic carbonyl compounds have been investigated as a means of developing new metal-carbon bond-forming reactions. Benzaldehyde and 1 react over 2 weeks at 5°C to give the silyloxyalkyl complex (CO)5MnCH(C6H5)OSi(CH3)3 (2) in 65-90% yield, depending upon conditions. Complex 2 undergoes rapid homolysis at 80°C to [(CO)5Mn]2 and the diastereomeric pinacol ethers [-CH(C6H5)OSi(CH3)3]2 (3a, 3b). Reactions of 1 with p-methoxybenzaldehyde and p-(dimethylamino)benzaldehyde are much faster but yield organometallic products which are much less stable toward homolysis. Compound 1 and butyraldehyde react to yield (CO)5MnH and the E and Z isomers (3:2 ratio) of butyraldehyde trimethylsilyl enol ether (8, 9). The isolation of (CO)5MnCOCH(n-C3H7)OSi(CH3) 3 (14) when this reaction is conducted under 10 atm of CO provides good evidence for the intermediacy of (CO)5MnCH(n-C3H7)OSi(CH3) 3. Acetone, cyclohexanone, and 2-methylcyclohexanone similarly react with 1 to yield (CO)5MnH and trimethylsilyl enol ethers. In the latter case, a mixture of regioisomers is formed which equilibrate due to the (CO)5MnH present. These reactions are suggested to proceed via rate-determining formation of ion pairs (CO)5Mn-+CR(R′)OSi(CH3)3. The thermodynamics and relevance of these reactions to catalytic hydrosilylation processes are discussed.

Reactions of (CO)5MnSi(CH3)3 and CO with aldehydes and cyclic ethers. Syntheses of functionalized pentacarbonylmanganese acyls and homologated organic compounds

Reactions of (CO)5MnSi(CH3)3 (1) and CO with aldehydes RCHO and cyclic ethers OCH2(CH2)nCH2 (n = 0-2) give manganese acyls (CO)5MnCOCH(R)OSi(CH3)3 and (CO)5MnCOCH2(CH2)nCH 2OSi(CH3)3 (n = 0, 6; n = 1, 9; n = 2, 10) in 26-72% and 54-87% yields, respectively. Experiments conducted in the absence of CO show that these transformations proceed via labile alkyl intermediates (CO)5MnCH(R)OSi(CH3)3 and (CO)5MnCH2(CH2)nCH 2OSi(CH3)3. Reactions of propylene oxide and cyclohexene oxide with 1 and CO give the manganese acyls expected from SN2 ring opening. When the reaction of 1 with aldehydes is conducted in the presence of (CO)5MnH under careful conditions, homologated aldehydes (CH3)3SiOCHRCHO form in 55-78% yields. Reaction of 1 and (CO)5MnH with oxetane gives (CH3)3-SiOCH2CH2CH2CHO (13, 38%) and (CH3)3SiOCHCH2CH2CH2O (14, 59%). Reaction of 9 and 10 with [(CH3CH2)2N]3S+Si(CH 3)3F2- yields γ-butyrolactone (84-95%) and δ-valerolactone (60-85%), respectively. The mechanisms of these transformations, and their utility in organic and organometallic synthesis, are discussed.