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19435352

Source:http://linkedlifedata.com/resource/pubmed/id/19435352

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pubmed-article:19435352rdf:typepubmed:Citationlld:pubmed
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pubmed-article:19435352pubmed:issue22lld:pubmed
pubmed-article:19435352pubmed:dateCreated2009-6-3lld:pubmed
pubmed-article:19435352pubmed:abstractTextThe novel disilazane compound 2-pyridinetetramethyldisilazane (1) has been synthesized. The competition between N-pyridine coordination and Si-H bond activation was studied through its reactivity with two ruthenium complexes. The reaction between 1 and RuH(2)(H(2))(2)(PCy(3))(2) led to the isolation of the new complex RuH(2){(eta(2)-HSiMe(2))N(kappaN-C(5)H(4)N)(SiMe(2)H)}(PCy(3))(2) (2) resulting from the loss of two dihydrogen ligands and coordination of 1 to the ruthenium center via a kappa(2)N,(eta(2)-Si-H) mode. Complex 2 has been characterized by multinuclear NMR experiments ((1)H, (31)P, (13)C, (29)Si), X-ray diffraction and DFT studies. In particular, the HMBC (29)Si-(1)H spectrum supports the presence of two different silicon environments: one Si-H bond is dangling, whereas the other one is eta(2)-coordinated to the ruthenium with a J(SiH) value of 50 Hz. DFT calculations (B3PW91) were also carried out to evaluate the stability of the agostic species versus a formulation corresponding to a bis(sigma-Si-H) isomer and confirmed that N-coordination overcomes any stabilization that could be gained by the establishment of SISHA interactions. There is no exchange between the two Si-H bonds present in 2, as demonstrated by deuterium-labeling experiments. Heating 2 at 70 degrees C under vacuum for 24 h, leads to the formal loss of one equivalent of H(2) from 2 and formation of the 16-electron complex RuH{(SiMe(2))N(kappaN-C(5)H(4)N)(SiMe(2)H)}(PCy(3))(2) (3) formulated as a hydrido(silyl) species on the basis of multinuclear NMR experiments. The dehydrogenation reaction is fully reversible under dihydrogen atmosphere. Reaction of Ru(COD)(COT) with 3 equiv of 1 under a H(2) pressure led to the isolation of the new complex RuH{(SiMe(2))N(kappaN-C(5)H(4)N)(SiMe(2)H)}(3) (4) characterized as a hydridotrisilyl complex by multinuclear NMR techniques, X-ray and neutron diffractions, as well as DFT calculations. The (29)Si HMBC experiments confirm the presence of two different silicon atoms in 4, with a signal at -14.64 ppm for three dangling Si-Me(2)H fragments and a signal at 64.94 ppm (correlating with the hydride signal) assigned to three Si-Me(2)N groups bound to Ru. Comparison of DFT and neutron parameters involving the hydride clearly indicates an excellent correlation. The Si-H distance of approximately 2.15 A is much shorter than the sum of the van der Waals radii and typically in the range of a significant interaction between a silicon and a hydrogen atom (SISHA interactions). In 4, three dangling Si-H groups remain accessible for further functionalization.lld:pubmed
pubmed-article:19435352pubmed:languageenglld:pubmed
pubmed-article:19435352pubmed:journalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:19435352pubmed:statusPubMed-not-MEDLINElld:pubmed
pubmed-article:19435352pubmed:monthJunlld:pubmed
pubmed-article:19435352pubmed:issn1520-5126lld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:MaceyG PGPlld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:Sabo-EtienneS...lld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:BarthelatJean...lld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:CoppelYannick...lld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:VendierLaureLlld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:AlbinatiAlber...lld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:GrellierMaryMlld:pubmed
pubmed-article:19435352pubmed:authorpubmed-author:AyedTahraTlld:pubmed
pubmed-article:19435352pubmed:issnTypeElectroniclld:pubmed
pubmed-article:19435352pubmed:day10lld:pubmed
pubmed-article:19435352pubmed:volume131lld:pubmed
pubmed-article:19435352pubmed:ownerNLMlld:pubmed
pubmed-article:19435352pubmed:authorsCompleteYlld:pubmed
pubmed-article:19435352pubmed:pagination7633-40lld:pubmed
pubmed-article:19435352pubmed:year2009lld:pubmed
pubmed-article:19435352pubmed:articleTitleVersatile coordination of 2-pyridinetetramethyldisilazane at ruthenium: Ru(II) vs Ru(IV) as evidenced by NMR, X-ray, neutron, and DFT studies.lld:pubmed
pubmed-article:19435352pubmed:affiliationCNRS, Laboratoire de Chimie de Coordination, 205 route de Narbonne, F-31077 Toulouse, France. grellier@lcc-toulouse.frlld:pubmed
pubmed-article:19435352pubmed:publicationTypeJournal Articlelld:pubmed