Synthesis and Crystal Structure of Cis [Pd {Ph2PCH2C (O) Ph} 2]-[BF4][B2F7]. Unexpected Formation and First Structural Characterisation of the Heptafluorodiborate Anion B2F7

Title:
Synthesis and Crystal Structure of Cis [Pd {Ph2PCH2C (O) Ph} 2]-[BF4][B2F7]. Unexpected Formation and First Structural Characterisation of the Heptafluorodiborate Anion B2F7
Authors:
Braunstein, P.; Douce, L.; Fischer, J.; Craig, Norman C.; Goetz-Grandmont, G.; Matt, D.
Abstract:
The reaction of cis-[Pd{Ph2PCH-C(O)Ph}2] (1) with HBF4/H2O instantly leads to the formation of the cationic complex cis-[Pd{Ph2PCH-C(O)Ph}2][BF4]2. When 1 was treated with commercial BF3·Et2O, containing HBF4 as an impurity, the related compound cis-[Pd{Ph2PCH-C(O)Ph}2][BF4][B2F7](2) was formed. The structure of 2 was determined by an X-ray diffraction study. The compound ctystallizes in the orthorhombic system, P212121 space group, Z=4, cell dimensions: a=16.474(4), b=19.007(5), c=12.932(4) Å, V=4049.3 Å3, final R=0.030. The two chelating phosphines define puckered five membered metallocycles characterised by PCH2 carbon atoms lying significantly out of the metal coordination plane (−0.617(7) Å for C1 and +0.779(7) Å for C21). This study establishes the first structural data for the B2F7− anion: the value of the BFbridgeB angle is 128.1(7)°. The values of the BFbridge bond lengths (1.50(1) and 1.51(1) Å are significantly longer than the other BF bonds (1.34–1.39 Å).
Citation:
Braunstein, P., L. Douce, J. Fischer, N.C. Craig, G. Goetz-Grandmont, and D. Matt. 1992. "Synthesis and Crystal Structure of Cis [Pd {Ph2PCH2C (O) Ph} 2]-[BF4][B2F7]. Unexpected Formation and First Structural Characterisation of the Heptafluorodiborate Anion B2F7." Inorganica Chimica Acta 194(2): 151-156.
Publisher:
Elsevier
DATE ISSUED:
1992
Department:
Chemistry
Type:
Article
PUBLISHED VERSION:
10.1016/S0020-1693(00)82656-0
PERMANENT LINK:
http://hdl.handle.net/11282/334089

Full metadata record

DC FieldValue Language
dc.contributor.authorBraunstein, P.en
dc.contributor.authorDouce, L.en
dc.contributor.authorFischer, J.en
dc.contributor.authorCraig, Norman C.en
dc.contributor.authorGoetz-Grandmont, G.en
dc.contributor.authorMatt, D.en
dc.date.accessioned2014-11-10T14:13:42Z-
dc.date.available2014-11-10T14:13:42Z-
dc.date.issued1992en
dc.identifier.citationBraunstein, P., L. Douce, J. Fischer, N.C. Craig, G. Goetz-Grandmont, and D. Matt. 1992. "Synthesis and Crystal Structure of Cis [Pd {Ph2PCH2C (O) Ph} 2]-[BF4][B2F7]. Unexpected Formation and First Structural Characterisation of the Heptafluorodiborate Anion B2F7." Inorganica Chimica Acta 194(2): 151-156.en
dc.identifier.issn0020-1693en
dc.identifier.urihttp://hdl.handle.net/11282/334089-
dc.description.abstractThe reaction of cis-[Pd{Ph2PCH-C(O)Ph}2] (1) with HBF4/H2O instantly leads to the formation of the cationic complex cis-[Pd{Ph2PCH-C(O)Ph}2][BF4]2. When 1 was treated with commercial BF3·Et2O, containing HBF4 as an impurity, the related compound cis-[Pd{Ph2PCH-C(O)Ph}2][BF4][B2F7](2) was formed. The structure of 2 was determined by an X-ray diffraction study. The compound ctystallizes in the orthorhombic system, P212121 space group, Z=4, cell dimensions: a=16.474(4), b=19.007(5), c=12.932(4) Å, V=4049.3 Å3, final R=0.030. The two chelating phosphines define puckered five membered metallocycles characterised by PCH2 carbon atoms lying significantly out of the metal coordination plane (−0.617(7) Å for C1 and +0.779(7) Å for C21). This study establishes the first structural data for the B2F7− anion: the value of the BFbridgeB angle is 128.1(7)°. The values of the BFbridge bond lengths (1.50(1) and 1.51(1) Å are significantly longer than the other BF bonds (1.34–1.39 Å).en
dc.language.isoen_USen
dc.publisherElsevieren
dc.identifier.doi10.1016/S0020-1693(00)82656-0en
dc.subject.departmentChemistryen
dc.titleSynthesis and Crystal Structure of Cis [Pd {Ph2PCH2C (O) Ph} 2]-[BF4][B2F7]. Unexpected Formation and First Structural Characterisation of the Heptafluorodiborate Anion B2F7en
dc.typeArticleen
dc.identifier.journalInorganica Chimica Actaen
dc.identifier.volume194en
dc.identifier.issue2en
dc.identifier.startpage151en
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