Publications

BibTex format

@article{Apps:2018:10.1039/c8dt02471e,
author = {Apps, SL and White, AJP and Miller, PW and Long, NJ},
doi = {10.1039/c8dt02471e},
journal = {Dalton Transactions},
pages = {11386--11396},
title = {Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex},
url = {http://dx.doi.org/10.1039/c8dt02471e},
volume = {47},
year = {2018}
}

Download

RIS format (EndNote, RefMan)

TY  - JOUR
AB  - 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.
AU  - Apps,SL
AU  - White,AJP
AU  - Miller,PW
AU  - Long,NJ
DO  - 10.1039/c8dt02471e
EP  - 11396
PY  - 2018///
SN  - 1477-9234
SP  - 11386
TI  - Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex
T2  - Dalton Transactions
UR  - http://dx.doi.org/10.1039/c8dt02471e
UR  - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000442509700013&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
UR  - http://hdl.handle.net/10044/1/64155
VL  - 47
ER  -

Download

DrPhilipMiller

Contact

Location

Summary

Citation

BibTex format

RIS format (EndNote, RefMan)