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Aminocarbyne Coupling Reactions at M(Ph2PCH2CH2PPh2)2 (M = Mo or W) Sites. Detailed Mechanistic Studies on the Protonation of Co-ordinated Isocyanides and Coupling of Ligands in trans- (X = t-Bu or Me)

DOI: 10.1039/DT9950001193

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1193 - 1200 (1995)

Update date:2022-08-03

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Authors:

Henderson, Richard A.Henderson, Richard A.

Pombeiro, Armando J. L.Pombeiro, Armando J. L.

Richards, Raymond L.Richards, Raymond L.

Silva, Joao J. R. Frausto daSilva, Joao J. R. Frausto da

Wang, YuWang, Yu

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Article abstract of DOI:10.1039/DT9950001193

The mechanism of protonation of trans- (M = Mo or W, R = Me or t-Bu, dppe = Ph2PCH2CH2PPh2) has been shown to involve the initial rapid protonation of an isocyanide ligand to form trans-(1+) which can then undergo rate-limiting intramolecular migration of the hydrogen to form (1+).For trans- an additional acid-catalysed pathway is observed involving the intermediate (2+) which subsequently rapidly releases a proton from the aminocarbyne to produce the hydrido complex.The formation of the diaminoacetylene complex, trans-2-MeHNCCNHMe)(dppe)2>(2+) occurs in three distinct steps.First is the rapid protonation of the isocyanide ligand to form trans-(2+), which at low concentrations of acid undergoes intramolecular hydrogen migration to produce the hydrido complex but at high acid concentrations rapidly forms trans-(2+).It is this bis(aminocarbyne) species which in the second step is attacked by Cl(1-) and subsequently undergoes intramolecular trans to cis isomerisation followed by coupling of the aminocarbyne ligands to form the product, trans-2-MeHNCCNHMe)(dppe)2>(1+).

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Product name:MoH(CNC(CH3)3)2((C6H5)2PCH2CH2P(C6H5)2)2(1+)*Cl(1-)=[MoH(CNC(CH3)3)2((C6H5)2PCH2CH2P(C6H5)2)2]Cl

Cas No:165750-12-9

165750-12-9

R&D Labs maybe for 165750-12-9

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