2017
DOI: 10.1246/bcsj.20170197
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Abstract: We have now found that molybdenumiodide complexes bearing a PNP-pincer ligand have a higher catalytic activity than the so far reported molybdenumdinitrogen complexes for ammonia formation from nitrogen gas under ambient reaction conditions, up to 830 equiv being produced based on a dinitrogen-bridged dimolybdenum complex (415 equiv of ammonia based on the molybdenum atom). This remarkable catalytic activity is induced by a novel reaction pathway, where the generation of a dinitrogen-bridged dimolybdenumiodide… Show more

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Cited by 165 publications
(237 citation statements)
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“…[5,6] Another challenge is the kinetically complex dinitrogen (N 2 )r eductionp rocess, which involves multiple electron transfers and complex intermediates. [8,9] Accordingly, alternative approaches to ammonia synthesis under more benign conditions are attractive in terms of as ustainable and decentralized ammonia industry.C ertain bacteria are able to convert N 2 into NH 3 with the use of the nitrogenase enzyme under mild conditions;t his has motivated researchers to explore various strategies for artificial nitrogen fixation, which include homogeneous catalysis on metal-dinitrogen complexes, [10,11] photocatalytic routes on semiconductors, [12] bioelectrochemical methods, [13] ande lectrochemical methods. The current Haber-Bosch process also requires ac ontinuous supplyo fu ltrapure hydrogen, which is almoste xclusively produced from fossil fuels, leads to as ubstantial amount of CO 2 emissions, and requires highly centralized distributions.…”
Section: Introductionmentioning
confidence: 99%
“…[5,6] Another challenge is the kinetically complex dinitrogen (N 2 )r eductionp rocess, which involves multiple electron transfers and complex intermediates. [8,9] Accordingly, alternative approaches to ammonia synthesis under more benign conditions are attractive in terms of as ustainable and decentralized ammonia industry.C ertain bacteria are able to convert N 2 into NH 3 with the use of the nitrogenase enzyme under mild conditions;t his has motivated researchers to explore various strategies for artificial nitrogen fixation, which include homogeneous catalysis on metal-dinitrogen complexes, [10,11] photocatalytic routes on semiconductors, [12] bioelectrochemical methods, [13] ande lectrochemical methods. The current Haber-Bosch process also requires ac ontinuous supplyo fu ltrapure hydrogen, which is almoste xclusively produced from fossil fuels, leads to as ubstantial amount of CO 2 emissions, and requires highly centralized distributions.…”
Section: Introductionmentioning
confidence: 99%
“…This total turnover number exceeds that of previously reported Fe catalysts, regardless of protocol, 19 and also exceeds TON data for most Mo catalysts. 1 Noteworthy exceptions concern recent Mo catalysts supported by pincer-phosphine ligands, which have been shown to be both very active and selective for NH 3 generation under certain conditions. 1d,f …”
mentioning
confidence: 99%
“…1 Noteworthy exceptions concern recent Mo catalysts supported by pincer-phosphine ligands, which have been shown to be both very active and selective for NH 3 generation under certain conditions. 1d,f …”
mentioning
confidence: 99%
“…Based on intensive study of the preparation of various transition-metal dinitrogen complexes and their detailed reactivity, [1] Schrock and co-workers discovered adirect and catalytic transformation of molecular dinitrogen into ammonia under ambient reaction conditions using am ononuclear molybdenum dinitrogen complex as ac atalyst. [3,4] After the seminal report of more-effective molybdenumcatalyzed dinitrogen reduction under ambient reaction conditions, [5] iron-, [6][7][8] cobalt-, [9,10] osmium-, [11] and ruthenium [11] catalyzed dinitrogen reductions under mild reaction conditions have been developed, where av ery low reaction temperature such as À78 8 8Ci sn ecessary to avoid the direct reaction of reducing reagents with proton sources.T he produced amounts of ammonia and hydrazine depend on the nature of the metals,l igands,a nd solvents.H owever, successful examples have been limited to the use of mid-tolate transition-metal complexes as catalysts.Early-transitionmetal-catalyzed dinitrogen reduction under mild reaction conditions has not been reported to date. [3,4] After the seminal report of more-effective molybdenumcatalyzed dinitrogen reduction under ambient reaction conditions, [5] iron-, [6][7][8] cobalt-, [9,10] osmium-, [11] and ruthenium [11] catalyzed dinitrogen reductions under mild reaction conditions have been developed, where av ery low reaction temperature such as À78 8 8Ci sn ecessary to avoid the direct reaction of reducing reagents with proton sources.T he produced amounts of ammonia and hydrazine depend on the nature of the metals,l igands,a nd solvents.H owever, successful examples have been limited to the use of mid-tolate transition-metal complexes as catalysts.Early-transitionmetal-catalyzed dinitrogen reduction under mild reaction conditions has not been reported to date.…”
mentioning
confidence: 99%