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Statements

Subject Item
n2:RIV%2F00216208%3A11310%2F13%3A10189979%21RIV14-MSM-11310___
rdf:type
n7:Vysledek skos:Concept
rdfs:seeAlso
http://dx.doi.org/10.1016/j.jorganchem.2013.02.010
dcterms:description
The bimetalladodecaborane cluster compound [(PMe2Ph)(4)Pt2B10H10] 1, quantitatively reacts with EtNC at room temperature to afford [{(EtNC)(PMe2Ph)(3)}(mu-EtNC) Pt2B10H10] 3 in which one molecule of EtNC replaces a terminal PMe2Ph ligand, and a second molecule of EtNC bridges the PtePt vector. The metalbridging EtNC molecule can be ejected from 3, either by irradiation with UV light, or via displacement with CO to form [{(EtNC)(PMe2Ph)(3)}(mu-CO) Pt2B10H10] 4. The CO-bridge may then in turn be replaced with SO2 to give [{(EtNC)(PMe2Ph)(3)}(mu-SO2) Pt2B10H10] 5. If 3 is allowed to react directly with SO2 then the SO2 molecule takes up a bridging position and the bridging EtNC displaces a terminal metal-bound phosphine to afford [{(EtNC)(2)(PMe2Ph)(2)}(mu-SO2) Pt2B10H10] 6. The transient absorption spectrum of 3 under UV illumination is investigated and shows that the bridging isonitrile is ejected to produce a transient spectrum very similar to that of [(PMe2Ph)(4)Pt2B10H10] 1. Reaction of [(PMe2Ph)(4)Pd2B10H10] 7, viz. the dipalladium analogue of 1, with EtNC results in the displacement of two PMe2Ph phosphine ligands forming [{(EtNC)(2)(PMe2Ph)(2)} Pd2B10H10] 8, which has no bridging EtNC unit and which shows only a weak ability to form an adduct with SO2. DFT calculations at the B3LYP/6-31G* level mirror the observed data well. (C) 2013 Elsevier B. V. All rights reserved. The bimetalladodecaborane cluster compound [(PMe2Ph)(4)Pt2B10H10] 1, quantitatively reacts with EtNC at room temperature to afford [{(EtNC)(PMe2Ph)(3)}(mu-EtNC) Pt2B10H10] 3 in which one molecule of EtNC replaces a terminal PMe2Ph ligand, and a second molecule of EtNC bridges the PtePt vector. The metalbridging EtNC molecule can be ejected from 3, either by irradiation with UV light, or via displacement with CO to form [{(EtNC)(PMe2Ph)(3)}(mu-CO) Pt2B10H10] 4. The CO-bridge may then in turn be replaced with SO2 to give [{(EtNC)(PMe2Ph)(3)}(mu-SO2) Pt2B10H10] 5. If 3 is allowed to react directly with SO2 then the SO2 molecule takes up a bridging position and the bridging EtNC displaces a terminal metal-bound phosphine to afford [{(EtNC)(2)(PMe2Ph)(2)}(mu-SO2) Pt2B10H10] 6. The transient absorption spectrum of 3 under UV illumination is investigated and shows that the bridging isonitrile is ejected to produce a transient spectrum very similar to that of [(PMe2Ph)(4)Pt2B10H10] 1. Reaction of [(PMe2Ph)(4)Pd2B10H10] 7, viz. the dipalladium analogue of 1, with EtNC results in the displacement of two PMe2Ph phosphine ligands forming [{(EtNC)(2)(PMe2Ph)(2)} Pd2B10H10] 8, which has no bridging EtNC unit and which shows only a weak ability to form an adduct with SO2. DFT calculations at the B3LYP/6-31G* level mirror the observed data well. (C) 2013 Elsevier B. V. All rights reserved.
dcterms:title
Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaborane clusters Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaborane clusters
skos:prefLabel
Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaborane clusters Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaborane clusters
skos:notation
RIV/00216208:11310/13:10189979!RIV14-MSM-11310___
n7:predkladatel
n8:orjk%3A11310
n4:aktivita
n21:P n21:I
n4:aktivity
I, P(GAP207/11/0705), P(GAP207/11/1577), P(GAP208/10/1678)
n4:cisloPeriodika
December
n4:dodaniDat
n15:2014
n4:domaciTvurceVysledku
n20:3157962
n4:druhVysledku
n19:J
n4:duvernostUdaju
n10:S
n4:entitaPredkladatele
n16:predkladatel
n4:idSjednocenehoVysledku
81322
n4:idVysledku
RIV/00216208:11310/13:10189979
n4:jazykVysledku
n18:eng
n4:klicovaSlova
nanosecond transient absorption spectroscopy; carbon monoxide; isonitrile; DFT; sequestration; small molecule; metallaboranes
n4:klicoveSlovo
n5:metallaboranes n5:sequestration n5:isonitrile n5:nanosecond%20transient%20absorption%20spectroscopy n5:carbon%20monoxide n5:DFT n5:small%20molecule
n4:kodStatuVydavatele
NL - Nizozemsko
n4:kontrolniKodProRIV
[C75A882BBB8F]
n4:nazevZdroje
Journal of Organometallic Chemistry
n4:obor
n12:CA
n4:pocetDomacichTvurcuVysledku
1
n4:pocetTvurcuVysledku
8
n4:projekt
n14:GAP207%2F11%2F1577 n14:GAP207%2F11%2F0705 n14:GAP208%2F10%2F1678
n4:rokUplatneniVysledku
n15:2013
n4:svazekPeriodika
747
n4:tvurceVysledku
Bould, Jonathan Lang, Kamil Macias, Ramon Londesborough, Michael Geoffrey Stephen Kubát, Pavel Winter, Rudolph E. K. Kennedy, John D. Císařová, Ivana
n4:wos
000326116500011
s:issn
0022-328X
s:numberOfPages
9
n17:doi
10.1016/j.jorganchem.2013.02.010
n11:organizacniJednotka
11310