Novel RhCp*/GaCp* and RhCp*/InCp* cluster complexes

The synthesis and structural characterization of the novel homoleptic cluster complexes [Pd2(GaCp*)2(mu2-GaCp*)3] (1c), [Pd3(GaCp*)4(mu2-GaCp*)4] (2b) and [Pd3(AlCp*)2(mu2-AlCp*)2(mu3-AlCp*)2] (3) (Cp*=C5Me5) are presented. Furthermore, ligand exchange reactions of these cluster complexes are explored. In contrast to the electronically and sterically saturated complexes [M(ECp*)4] (M=Ni, Pd, Pt), the new unsaturated analogues [M(a)(ER)b] (E=Al, Ga, In) react with a variety of typical ligands (Cp*Al, CO, phosphines, isonitriles) to give new di- and tri-substituted compounds like [Pt2(GaCp*)2(mu2-AlCp*)3] (1d), [PdPt(GaCp*)(PPh3)(mu2-GaCp*)3] (4b), or [Pd3(PPh3)3(mu2-InCp*)(mu3-InCp*)2] (8). The trends of the reactivity of [M(a)(ER)b] as well as their fluxional behavior in solution has been elucidated by NMR spectroscopy, resulting in a mechanistic rationale for the ligand exchange reactions as well as the fluxional processes.

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“…No exchange of free to coordinated ligand is observed on the NMR timescale. The coordinated CO gives rise to a 13 …”

Section: Resultsmentioning

confidence: 99%

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

Steinke

Gemel

Winter

et al. 2005

Chemistry A European J

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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. However, the reaction of 1 with Na(mt) yielded only a complex mixture.…”

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

confidence: 90%

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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“…Structure of the cation in 2 (thermal ellipsoids are shown with 50 % probability, hydrogen atoms have been omitted for clarity). Selected bond lengths [pm] and angles [8]: Rh-Ga1 247.11 (10), Rh-Ga2 230.99 (7), Rh-Ga4 228.15 (6), Rh-Ga5 228.15 (6), Rh-Ga3 230.99 (7), , Ga1-Ga2 276.61 (13), Ga1-Ga5 286.83 (13); C1-Ga1-Rh 176.1(5), Ga1-Rh-Ga3 163.58(4), Ga2-Rh-Ga4 107.91(2), Ga4-RhGa5 119.59(4).…”

Section: Rh]mentioning

confidence: 99%

Methylgallium as a Terminal Ligand in [(Cp*Ga)₄Rh(GaCH₃)]⁺

Cadenbach¹,

Gemel²,

Zacher³

et al. 2008

Angew Chem Int Ed

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The smallest possible gallium alkyl species, the otherwise elusive GaCH3, has been generated by protolytic cleavage of Cp*H from a coordinated a {Ga(CH3)Cp*} moiety and trapped in the title complex (see structure; C white, Ga blue, Rh brown). The counterintuitive shortening of the RhGaCH3 bond upon adduct formation with pyridine illustrates that bond lengths alone are insufficient for the assignment of bond order.

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Novel RhCp/GaCp and RhCp/InCp cluster complexes

Cited by 66 publications

References 42 publications

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

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

Methylgallium as a Terminal Ligand in [(Cp*Ga)₄Rh(GaCH₃)]⁺

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Novel RhCp*/GaCp* and RhCp*/InCp* cluster complexes

Cited by 66 publications

References 42 publications

The Clusters [Ma(ECp*)b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

The Clusters [Ma(ECp*)b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

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

Methylgallium as a Terminal Ligand in [(Cp*Ga)4Rh(GaCH3)]+

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Novel RhCp/GaCp and RhCp/InCp cluster complexes

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

The Clusters [M_a(ECp*)_b] (M=Pd, Pt; E=Al, Ga, In): Structures, Fluxionality, and Ligand Exchange Reactions

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

Methylgallium as a Terminal Ligand in [(Cp*Ga)₄Rh(GaCH₃)]⁺