Home >> Canadian Journal of Chemistry, Volume 83, Number 4

Portability of the RNNMo(3+) core — Application to the synthesis of dinitrogen-derived trialkoxymolybdenum organodiazenido complexes

Authors: Cherry, John-Paul F.; Diaconescu, Paula L.; Cummins, Christopher C.

Source: Canadian Journal of Chemistry, Volume 83, Number 4, April 2005 , pp. 302-307(6)

Publisher: NRC Research Press

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Abstract:

An alcoholysis strategy has been employed in the synthesis of new oligo- or polymeric trialkoxymolybdenum diazenido complexes [R1NNMo(O-1-Ad)3]x (R1 = Me or C(O)OMe) as well as their mononuclear THF solvates R1NNMo(O-1-Ad)3(THF). Dinitrogen-derived diazenido precursor complexes R1NNMo(N[R]Ar)3 (R = i-Pr, Ar = 3,5-C6H3Me2) react smoothly with 3 equiv. 1-adamantanol to liberate 3 equiv. HN(R)Ar without disruption of the diazenidomolybdenum(3+) core. X-ray structural investigations were carried out for diazenido complex MeNNMo(O-1-Ad)3(THF) and for the corresponding cationic dimethyldiazenido complex [Me2NNMo(O-1-Ad)3(THF)]+, obtained as its triflate salt. The latter cation was found upon cobaltocene reduction to undergo N—N bond cleavage, producing nitride NMo(O-1-Ad)3 (synthesized independently) and dimethylamine. Key words: molybdenum, dinitrogen, bond cleavage, hydrazido, diazenido.

On a utilisé une stratégie d'alcoolyse dans la synthèse de nouveaux complexes oligo- et polymériques du diazénido trialkoxymolybdène [R1NNMo(O-1-Ad)3]x (R1 = Me ou C(O)OMe) et celle de leurs complexes monomoléculaires monosolvatés par le THF R1NNMo(O-1-Ad)3(THF). Les complexes précurseurs diazénido dérivés du diazote R1NNMo(N[R]Ar)3 (R = i-Pr, Ar = 3,5-C6H3Me2) réagissent sans problème avec trois équivalents d'adamant-1-ol pour libérer trois équivalents de HN(R)Ar sans disruption du noyau diazénidomolybdène(3+). On a examiné les structures du complexe diazénido MeNNMo(O-1-Ad)3(THF) et du complexe diméthyldiazénido cationique correspondant [Me2NNMo(O-1-Ad)3(THF)]+ isolé sous la forme de triflate. On a trouvé que la réduction de ce dernier cation par le cobaltocène conduit à un clivage de la liaison N—N qui conduit à la formation du nitrure NMo(O-1-Ad)3 (qui a été synthétisé par une voie indépendante) et de la diméthylamine.Mots clés : molybdène, diazote, clivage d'une liaison, hydrazido, diazénido.[Traduit par la Rédaction]

Document Type: Research article

Publication date: 2005-04-01

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  • Published since 1929, this monthly journal reports current research findings in all branches of chemistry. It includes the traditional areas of analytical, inorganic, organic, and physical-theoretical chemistry and newer interdisciplinary areas such as materials science, spectroscopy, chemical physics, and biological, medicinal and environmental chemistry. Full papers, preliminary communications and review articles are all welcomed.
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