TY - JOUR
T1 - Magnesium(I) Reduction of CO and N2 Complexes of Cummins’ Molybdenum(III) Tris(anilide), [Mo(L){N(Ar’)But}3] (L=CO or N2; Ar’=3,5-dimethylphenyl)
AU - Yuvaraj, K.
AU - Paparo, Albert
AU - Matthews, Aidan J.R.
AU - Jones, Cameron
N1 - Funding Information:
CJ is grateful to the Australian Research Council for funding part of this work. Moreover, this material is based upon work supported by the Air Force Office of Scientific Research under award number FA2386‐21‐1‐4048.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2021/12/21
Y1 - 2021/12/21
N2 - Reductions of the in situ generated CO and N2 complexes of Cummins’ molybdenum(III) tris(anilide) complex, viz. [Mo(L){N(Ar’)But}3] (L=CO or N2, Ar’=3,5-dimethylphenyl), using a dimagnesium(I) compound, [{(MesNacnac)Mg}2] (MesNacnac=[HC(MeCNMes)2]−, Mes=mesityl), are reported. Reduction of [Mo(CO){N(Ar’)But}3] afforded a mixture of products, three of which were isolated in low yield and crystallographically characterized. These were a molybdenum(II) tris(carbamoyl) complex, [(MesNacnac)Mg{μ-(O=)[But(Ar’)N]C}3Mo(CO)3] 1, a magnesium(II) carbamate, [{(MesNacnac)Mg[μ-O2CN(Ar’)But]}2] 2, and the 1,3-diamino-1,2,3-trione, But(Ar’)NC3(=O)3N(Ar’)But 3. The mechanisms of formation of these products are speculated upon. The reduction of [Mo(N2){N(Ar’)But}3] with [{(MesNacnac)Mg}2], in the presence of the N-heterocyclic carbene, :C{N(Me)C(Me)}2 TMC, gave the heterobimetallic molybdenum(II) diazenido complex, [(MesNacnac)(TMC)Mg(μ-N2)Mo{N(Ar’)But}3] 4, in a low-moderate isolated yield. Reaction of this with chlorotrimethylsilane afforded an essentially quantitative yield of the known silyldiazenido complex, [(Me3SiN2)Mo{N(Ar’)But}3] 5.
AB - Reductions of the in situ generated CO and N2 complexes of Cummins’ molybdenum(III) tris(anilide) complex, viz. [Mo(L){N(Ar’)But}3] (L=CO or N2, Ar’=3,5-dimethylphenyl), using a dimagnesium(I) compound, [{(MesNacnac)Mg}2] (MesNacnac=[HC(MeCNMes)2]−, Mes=mesityl), are reported. Reduction of [Mo(CO){N(Ar’)But}3] afforded a mixture of products, three of which were isolated in low yield and crystallographically characterized. These were a molybdenum(II) tris(carbamoyl) complex, [(MesNacnac)Mg{μ-(O=)[But(Ar’)N]C}3Mo(CO)3] 1, a magnesium(II) carbamate, [{(MesNacnac)Mg[μ-O2CN(Ar’)But]}2] 2, and the 1,3-diamino-1,2,3-trione, But(Ar’)NC3(=O)3N(Ar’)But 3. The mechanisms of formation of these products are speculated upon. The reduction of [Mo(N2){N(Ar’)But}3] with [{(MesNacnac)Mg}2], in the presence of the N-heterocyclic carbene, :C{N(Me)C(Me)}2 TMC, gave the heterobimetallic molybdenum(II) diazenido complex, [(MesNacnac)(TMC)Mg(μ-N2)Mo{N(Ar’)But}3] 4, in a low-moderate isolated yield. Reaction of this with chlorotrimethylsilane afforded an essentially quantitative yield of the known silyldiazenido complex, [(Me3SiN2)Mo{N(Ar’)But}3] 5.
KW - Carbon monoxide
KW - Dinitrogen
KW - Magnesium
KW - Molybdenum
KW - Reductive activation
UR - http://www.scopus.com/inward/record.url?scp=85117173972&partnerID=8YFLogxK
U2 - 10.1002/ejic.202100815
DO - 10.1002/ejic.202100815
M3 - Article
AN - SCOPUS:85117173972
SN - 1434-1948
VL - 2021
SP - 4998
EP - 5003
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 47
ER -