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Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

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Title: Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex
Authors: Apps, SL
White, AJP
Miller, PW
Long, NJ
Item Type: Journal Article
Abstract: The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH2PPh2)3, NP3Ph) are reported. Reaction of N-triphos with [MoX3(THF)3] (X = Cl, Br, I) gave the Mo(III) complex [MoX3(κ2-NP3Ph)(THF)] (1), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N2)(dppm)(κ3-NP3Ph)] (2), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)2(dppm)(κ3-NP3Ph)] (4), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex 2. The reactivity of the dinitrogen complex 2 with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H+, BBr3 and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to 2 resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh2)(PCP)][B(C6F5)4] (7), where PCP, [Ph2PCNHCH2PPh2] is the carbenic ligand formed upon rearrangement from the reaction of 2 with M[B(C6F5)4] (M = Li, Na or K). Single crystal X-ray diffraction of complexes 1, 2, 4 and 7 provided structural confirmation of the N-triphos molybdenum complexes described.
Issue Date: 7-Sep-2018
Date of Acceptance: 23-Jul-2018
URI: http://hdl.handle.net/10044/1/64155
DOI: https://dx.doi.org/10.1039/c8dt02471e
ISSN: 1477-9234
Publisher: Royal Society of Chemistry
Start Page: 11386
End Page: 11396
Journal / Book Title: Dalton Transactions
Volume: 47
Issue: 33
Copyright Statement: © The Royal Society of Chemistry 2018
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
CATALYTIC-REDUCTION
TRIPOD LIGAND
N-2
AMMONIA
COORDINATION
ACTIVATION
HYDRAZINE
CHEMISTRY
NITROGEN
DONOR
0302 Inorganic Chemistry
0399 Other Chemical Sciences
Inorganic & Nuclear Chemistry
Publication Status: Published
Online Publication Date: 2018-07-23
Appears in Collections:Chemistry
Catalysis and Advanced Materials
Faculty of Natural Sciences