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Construction of frustrated Lewis pair from nitride and phosphine for the activation and cleavage of molecular hydrogen
Author(s) -
Christopher Jeyakumar Thayalaraj,
Deepa Masilamani,
Baskaran Sambath,
Sivasankar Chinnappan
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5811
Subject(s) - chemistry , adduct , frustrated lewis pair , phosphine , hydride , cleavage (geology) , reagent , molecule , lewis acids and bases , hydrogen , hydrogen bond , bond cleavage , nitride , photochemistry , medicinal chemistry , polymer chemistry , catalysis , organic chemistry , geotechnical engineering , layer (electronics) , fracture (geology) , engineering
Activation and cleavage of molecular hydrogen (H 2 ) to proton and hydride is an important task for several reasons, especially as a reagent in hydrogenation. In this scenario, with the support of density‐functional theory methods, a novel strategy has been devised for the conversion of coordinated nitride into ammonia using molecular hydrogen in the presence of tri‐ tert ‐butylphosphine (P t Bu 3 ). The proposed methodology is based on the formation of frustrated Lewis pair (FLP) from [Os VI (tpy)(Cl) 2 (N)] + (tpy = 2,2′:6′,2′′‐terpyridine) and P t Bu 3 followed by reaction with molecular hydrogen to form an FLP–H 2 adduct. The FLP–H 2 adduct can further undergo H–H bond cleavage heterolytically to produce proton and hydride which can be eventually used for the functionalization of coordinated nitride to ammonia. The calculated energy profile comprising all possible intermediates and transition‐state molecules suggests that the proposed reaction pathway is energetically viable at elevated temperatures.