Komplexe mit dativen Bindungen zwischen d‐ und s‐Block‐Metallen: Synthese und Struktur von [(Cy<sub>3</sub>P)<sub>2</sub>Pt‐Be(Cl)X] (X=Cl, Me)

Braunschweig, Holger; Gruß, Katrin; Radacki, Krzysztof

doi:10.1002/ange.200900521

Cited by 38 publications

(17 citation statements)

References 42 publications

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“…Al III and Pt 0 !Be II ), [10] and Fischer et al (Rh I !Ga III ). [11] Armed with this knowledge together with the fact that we successfully synthesized several bimetallic complexes with Sn II !Pd II and Sn II !Pt II interactions, [12] we investigated the reactivity of the kinetically more robust complex cis-[Pt- 2 Cl 2 ] (1, Scheme 2), with the N^C^N-chelating ligand 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 À (hereafter denoted as L), [12c] towards the bridging mt ligand.…”

Section: Ligand These Reactions Yielded Trans-[pt(me)a C H T U N G Tmentioning

confidence: 94%

Intramolecularly Coordinated [{2,6‐(Me₂NCH₂)₂C₆H₃}Sn^II]⁺: A Strong σ Donor for Pt^II

Martincová¹,

Dostál²,

Herres‐Pawlis³

et al. 2011

Chemistry A European J

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The reactivity of the late transition metals (TM) towards Sn II X 2 , where X is NR 2 , an organic group, or a halide, is still of current interest due to the fact that tin(II) dichloride is an important cocatalyst in various late-transition-metal-catalyzed reactions, such as hydrogenations, hydroformylations, or isomerization.[1] Most of these reactions show the general behavior of Sn II X 2 insertion into TM À Cl bonds and usually yield complexes with the general formula TMÀSnX 2 Cl with weakly coordinated Sn II anions, which have been postulated to have a strong trans-labilizing effect. [1][2][3] The exact role of Sn II X 2 as a cocatalyst is, however, still unclear. Better understanding of the nature of the interaction of the Sn II species with late transition metals was provided by Deelman and co-workers who studied the interaction of SnCl 2 and a Pt II complex in the presence of a catalytically relevant 2-PyPPh 2 ligand. These reactions yielded trans-II atom as a self-assembled P^Sn^P pincer ligand (Scheme 1).[4] The interaction of Sn II !Pt II was thus further supported by two head-to-head coordinated 2-PyPPh 2 ligands in bridging positions in complex I and the same group extended the nature of this motif to Sn II !Pd II interactions in a subsequent work.[5]In addition, recently Wagler et al. reported a structurally related metallastannatrane, [PdSnA C H T U N G T R E N N U N G (m-mt) 4 Cl 2 ], in which the Pd II !Sn IV interaction is supported by four mt ligands (mt = 1-methyl-2-mercaptoimidazolide) [6] and the same group extended the nature of this motif to Pd II !Si IV and Pt II !Si IV dative bonds (Scheme 1, II).[7] However, these metals!metallatranes contain inverse interactions between late transition metals and main-group metals, in which the transition metals act as s donors to the Lewis acidic center of the main-group elements.[8] Similar systems with various TM-E interactions (E = main-group element) were also reported by Bourrisou et al. [11]Armed with this knowledge together with the fact that we successfully synthesized several bimetallic complexes with Sn II !Pd II and Sn II !Pt II interactions, [12] we investigated the reactivity of the kinetically more robust complex cis-[Pt-A C H T U N G T R E N N U N G ({2,6-A C H T U N G T R E N N U N G (Me 2 NCH 2 ) 2 C 6 H 3 }SnCl) 2 Cl 2 ] (1, Scheme 2), with the N^C^N-chelating ligand 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 À (hereafter denoted as L), [12c] towards the bridging mt ligand. However, the reaction of 1 with Na(mt) yielded only a complex mixture. On the other hand, reports dealing with the use of the pyridine-2-thionate (pyt) ligand (III, Scheme 1) in the Scheme 2. Synthesis of the mixture of complexes 2 and 3.

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Section: Ligand These Reactions Yielded Trans-[pt(me)a C H T U N G Tmentioning

confidence: 94%

Intramolecularly Coordinated [{2,6‐(Me₂NCH₂)₂C₆H₃}Sn^II]⁺: A Strong σ Donor for Pt^II

Martincová¹,

Dostál²,

Herres‐Pawlis³

et al. 2011

Chemistry A European J

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“…The increasing number and variety of structurally authenticated transition-metal complexes of boranes, alanes, and gallanes have given more insight into unusual M!ER 3 interactions (E = B, Al, Ga). [2][3] Here, the combination of donor and acceptor moieties within the same ligand architecture, so-called ambiphilic ligands, proved particularly efficient.…”

Section: Introductionmentioning

confidence: 99%

Hypervalent Silicon Compounds by Coordination of Diphosphine–Silanes to Gold

Gualco

Mercy

Ladeira³

et al. 2010

Chemistry A European J

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Coordination of ambiphilic diphosphine-silane ligands [o-(iPr(2)P)C(6)H(4)](2)Si(R)F (R=F, Ph, Me) to AuCl affords pentacoordinate neutral silicon compounds in which the metal atom acts as a Lewis base. X-ray diffraction analyses, NMR spectroscopy, and DFT calculations substantiate the presence of Au→Si interactions in these complexes, which result in trigonal-bipyramidal geometries around silicon. The presence of a single electron-withdrawing fluorine atom is sufficient to observe coordination of the silane as a σ-acceptor ligand, provided it is positioned trans to gold. The nature of the second substituent at silicon (R=F, Ph, Me) has very little influence on the magnitude of the Au→Si interaction, in marked contrast to N→Si adducts. According to variable-temperature and 2D EXSY NMR experiments, the apical/equatorial positions around silicon exchange in the slow regime of the NMR timescale. The two forms, with the fluorine atom in trans or cis position to gold, were characterized spectroscopically and the activation barrier for their interconversion was estimated. The bonding and relative stability of the two isomeric structures were assessed by DFT calculations.

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“…Based on previous success with the facile formation of "metal-only" Lewis pairs between electron-rich Pt 0 complexes and p-block metals, e. g. in the case of [(Cy 3 P) 2 2 Pt-BeCl 2 ] (1) comprising an unprecedented, electron precise bond between beryllium and a d-block metal [15]. Recent studies showed that related low-valent palladium complexes also show a propensity to act as metal bases towards metal-coordinate boryl and borylene ligands, and therefore behave similar to their platinum congeners [16 -19].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Characterization of the Dinuclear Beryllium Species [Be₂Cl₂(μ-Cl)₂(PCy₃)₂]

Braunschweig

Gruß

2011

Zeitschrift Für Naturforschung B

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Komplexe mit dativen Bindungen zwischen d‐ und s‐Block‐Metallen: Synthese und Struktur von [(Cy₃P)₂Pt‐Be(Cl)X] (X=Cl, Me)

Cited by 38 publications

References 42 publications

Intramolecularly Coordinated [{2,6‐(Me₂NCH₂)₂C₆H₃}Sn^II]⁺: A Strong σ Donor for Pt^II

Intramolecularly Coordinated [{2,6‐(Me₂NCH₂)₂C₆H₃}Sn^II]⁺: A Strong σ Donor for Pt^II

Hypervalent Silicon Compounds by Coordination of Diphosphine–Silanes to Gold

Synthesis and Structural Characterization of the Dinuclear Beryllium Species [Be₂Cl₂(μ-Cl)₂(PCy₃)₂]

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Komplexe mit dativen Bindungen zwischen d‐ und s‐Block‐Metallen: Synthese und Struktur von [(Cy3P)2Pt‐Be(Cl)X] (X=Cl, Me)

Cited by 38 publications

References 42 publications

Intramolecularly Coordinated [{2,6‐(Me2NCH2)2C6H3}SnII]+: A Strong σ Donor for PtII

Intramolecularly Coordinated [{2,6‐(Me2NCH2)2C6H3}SnII]+: A Strong σ Donor for PtII

Hypervalent Silicon Compounds by Coordination of Diphosphine–Silanes to Gold

Synthesis and Structural Characterization of the Dinuclear Beryllium Species [Be2Cl2(μ-Cl)2(PCy3)2]

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Komplexe mit dativen Bindungen zwischen d‐ und s‐Block‐Metallen: Synthese und Struktur von [(Cy₃P)₂Pt‐Be(Cl)X] (X=Cl, Me)

Intramolecularly Coordinated [{2,6‐(Me₂NCH₂)₂C₆H₃}Sn^II]⁺: A Strong σ Donor for Pt^II

Intramolecularly Coordinated [{2,6‐(Me₂NCH₂)₂C₆H₃}Sn^II]⁺: A Strong σ Donor for Pt^II

Synthesis and Structural Characterization of the Dinuclear Beryllium Species [Be₂Cl₂(μ-Cl)₂(PCy₃)₂]