Linked Life Data

17050697

Source:http://linkedlifedata.com/resource/pubmed/id/17050697

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
46
pubmed:dateCreated
2006-11-19
pubmed:abstractText
Activation of molecular nitrogen by transition metal complexes is an area of current interest as investigations using the inert N2 molecule to produce higher-value organonitrogen compounds intensify. In an attempt to extend the addition of hydride reagents E-H (where E = BR2, AlR2, and SiR3) to the dinitrogen complex ([NPN]Ta)2(mu-H)2(mu-eta1:eta2-N2) [1; where NPN = (PhNSiMe2CH2)2PPh], the reaction with zirconocene chlorohydride, [Cp2Zr(Cl)H]x, was examined. The crystalline product formed in 35% yield was determined to be ([NP(N)N]Ta)(mu-H)2(mu-N)(Ta[NPN])(ZrCp2) (2) in which the coordinated N2 has been cleaved to form a phosphinimide bridging between Ta and Zr and a triply bridging nitride. The mechanism of this reaction was examined to determine the fate of the chloride and hydride ligands attached to Zr in the starting zirconocene reagent. Using the zirconocene dihydride dimer ([Cp2ZrH2]2), a higher yield of 2 was obtained (76%), and H2 was also observed by 1H NMR spectroscopy. To probe the origin of the eliminated H2, the dideuterated dinitrogen complex ([NPN]Ta)2(mu-D)2(mu-eta1:eta2-N2) (d2-1) was allowed to react with ([Cp2ZrH2]2), which resulted in the formation of ([NP(N)N]Ta)(mu-D)2(mu-N)(Ta[NPN])(ZrCp2), (d2-2), with no evidence of hydrogen for deuterium scrambling between the starting zirconocene dihydride and the ditantalum dinitrogen complex. Studies into the use of preformed Zr(II) and Ti(II) reagents were also performed. The proposed mechanism involves initial adduct formation that facilitates inner-sphere electron transfer to cleave the N-N bond to form a species with bridging nitrides, one of which is transformed by nucleophilic attack of a phosphine donor to generate the observed phosphinimide.
pubmed:commentsCorrections
http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-11457146, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-11825072, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-12105920, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-12215645, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-12552526, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-12630877, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-12642670, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-12817971, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-12843387, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-14765191, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-14871129, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-15149221, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-15291518, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-1529354, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-15521731, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-16159262, http://linkedlifedata.com/resource/pubmed/commentcorrection/17050697-16417385
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
0027-8424
pubmed:author
pubmed:issnType
Print
pubmed:day
14
pubmed:volume
103
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
17094-8
pubmed:dateRevised
2009-11-18
pubmed:meshHeading
pubmed:year
2006
pubmed:articleTitle
Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen.
pubmed:affiliation
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, Canada V6T 1Z1.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't