C‐H‐aktivierte Isomere von [M(AlCp*)<sub>5</sub>] (M=Fe, Ru)

Steinke, Tobias; Cokoja, Mirza; Gemel, Christian; Kempter, Andreas; Krapp, Andreas; Frenking, Gernot; Zenneck, Ulrich; Fischer, Roland A.

doi:10.1002/ange.200462834

Cited by 34 publications

(24 citation statements)

References 44 publications

(6 reference statements)

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“…CÀH activation of benzene and oxidative addition of HSiEt 3 takes place at the unsaturated intermediate [NiA C H T U N G T R E N N U N G (AlCp*) 3 ] [16] and related multiple C À H activation reactions at the methyl groups of the Cp* moiety possibly limit the accessibility of [MA C H T U N G T R E N N U N G (AlCp*) 5 ] (M= Fe, Ru). [17] The reaction of [RhCp*(L)-…”

Section: H T U N G T R E N N U N G (Ddp)} 2 (H)a C H T U N G T R E N mentioning

confidence: 99%

Pt⁰ and Pd⁰ Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [E^I(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

Kempter

Gemel

Fischer

2007

Chemistry A European J

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Various products of the reaction of [E(ddp)] (ddp=2-{(2,6-diisopropylphenyl)amino}-4-{(2,6-diisopropylphenyl)imino}-2-pentene; E=Al, Ga) with Pt(0) and Pd(0) olefin complexes are reported. Thus, the reaction of [Pt(cod)(2)] (cod=1,5-cyclooctadiene) with two equivalents of [Ga(ddp)] yields [Pt(1,3-cod){Ga(ddp)}(2)] (1), whereas treatment of [Pd(2)(dvds)(3)] (dvds=1,1,3,3-tetramethyl1,3-divinyldisiloxane) with [E(ddp)] leads to the monomeric compounds [(dvds)Pd{E(ddp)}] (E=Ga (2 a), Al (2 b)) by substitution of the bridging dvds ligand. Both 1 and 2 a readily react with strong pi-acceptor ligands such as CO or tBuNC to give the dimeric compounds [M{mu(2)-Ga(ddp)}(L)] (L=CO, tBuNC; M=Pt (3 a, 5 a), Pd (3 b, 5 b)), respectively. Based on (1)H NMR spectroscopic data, [Pt{Ga(ddp)}(2)(CO)] is likely to be an intermediate in the formation of 3 a. Furthermore, reactions of 1 with H(2) and HSiEt(3) yield the monomeric compounds [Pt{Ga(ddp)}(2)(H)(2)] (7) and [Pt{Ga(ddp)}(2)(H)(SiEt(3))] (8). Finally, the reaction of [Pt(cod)(2)] with one equivalent of [Ga(ddp)] in the presence of H(2) in hexane gives the new dimeric cluster [Pt{mu(2)-Ga(ddp)}(H)(2)](2) (9).

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Section: H T U N G T R E N N U N G (Ddp)} 2 (H)a C H T U N G T R E N mentioning

confidence: 99%

Pt⁰ and Pd⁰ Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [E^I(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

Kempter

Gemel

Fischer

2007

Chemistry A European J

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“…[5] In particular, the Al-Fe compound [Fe(AlCp*) 5 ] is already known. [28] Thus, more examples of the general type [A a B b ]R c , and even larger clusters (a + b @ c), may be discovered in the future. …”

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confidence: 97%

The Intermetalloid Cluster [(Cp*AlCu)₆H₄], Embedding a Cu₆ Core Inside an Octahedral Al₆ Shell: Molecular Models of Hume–Rothery Nanophases

et al. 2014

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Defined molecular models for the surface chemistry of Hume-Rothery nanophases related to catalysis are very rare. The Al-Cu intermetalloid cluster [(Cp*AlCu)6H4] was selectively obtained from the clean reaction of [(Cp*Al)4] and [(Ph3PCuH)6]. The stronger affinity of Cp*Al towards Cu sweeps the phosphine ligands from the copper hydride precursor and furnishes an octahedral Al6 cage to encapsulate the Cu6 core. The resulting hydrido cluster M12H4 reacts with benzonitrile to give the stoichiometric hydrometalation product [(Cp*AlCu)6H3(N=CHPh)].

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“…The shift of the hydride signal is well in agreement with terminal RuÀH complexes reported in literature. [25][26][27] In addition, the transversal relaxation time T1 of 2 has been determined to be above 300 ms, which clearly indicates the classical dihydride structure of 2. [28,29] Single crystals suitable for X-ray diffraction studies, were obtained by slowly cooling a saturated pentane solution of 2 down to À30 8C for several days.…”

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confidence: 99%

Organometallic Chemistry of Ga⁺: Formation of an Unusual Gallium Dimer in the Coordination Sphere of Ruthenium

Cadenbach

Gemel

Bollermann

et al. 2008

Chemistry A European J

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New insights into the distinct organometallic chemistry of the Ga(+) ion are presented. Ga(+) reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH(2))(3) (2-)) attached at Ru by insertion into a Ru--C bond. The resulting "gallamethylallyl" ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [{Ru(GaCp*)(3)[eta(3)-(CH(2))(2)C{CH(2)(mu-Ga)}]}(2)][(BAr(F))(2)] (4) (Cp*=C(5)Me(5), [BAr(F)]=[B{C(6)H(3)(CF(3))(2)}(4)]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga--Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga--Ga interaction. Finally, a novel example of a complex with substituent-free Ga(+) as a ligand was found in the compound [Ru(PCy(3))(2)(GaCp*)(2)(Ga)][BAr(F)] (6) (Cy=C(6)H(11), cyclohexyl), the very short Ru--Ga bond length confirming the assumption that Ga(+) represents a pure sigma/pi-accepting ligand in this case.

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C‐H‐aktivierte Isomere von [M(AlCp*)₅] (M=Fe, Ru)

Cited by 34 publications

References 44 publications

Pt⁰ and Pd⁰ Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [E^I(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

Pt⁰ and Pd⁰ Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [E^I(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

The Intermetalloid Cluster [(Cp*AlCu)₆H₄], Embedding a Cu₆ Core Inside an Octahedral Al₆ Shell: Molecular Models of Hume–Rothery Nanophases

Organometallic Chemistry of Ga⁺: Formation of an Unusual Gallium Dimer in the Coordination Sphere of Ruthenium

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C‐H‐aktivierte Isomere von [M(AlCp*)5] (M=Fe, Ru)

Cited by 34 publications

References 44 publications

Pt0 and Pd0 Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [EI(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

Pt0 and Pd0 Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [EI(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

The Intermetalloid Cluster [(Cp*AlCu)6H4], Embedding a Cu6 Core Inside an Octahedral Al6 Shell: Molecular Models of Hume–Rothery Nanophases

Organometallic Chemistry of Ga+: Formation of an Unusual Gallium Dimer in the Coordination Sphere of Ruthenium

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C‐H‐aktivierte Isomere von [M(AlCp*)₅] (M=Fe, Ru)

Pt⁰ and Pd⁰ Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [E^I(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

Pt⁰ and Pd⁰ Olefin Complexes of the Metalloid N‐Heterocyclic Carbene Analogues [E^I(ddp)] (ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene; E=Al, Ga): Ligand Substitution, HH and SiH Bond Activation, and Cluster Formation

The Intermetalloid Cluster [(Cp*AlCu)₆H₄], Embedding a Cu₆ Core Inside an Octahedral Al₆ Shell: Molecular Models of Hume–Rothery Nanophases

Organometallic Chemistry of Ga⁺: Formation of an Unusual Gallium Dimer in the Coordination Sphere of Ruthenium