Synthesis and characterization of platinum(II) complexes with terminal alkynes analogous to Zeise's salt — structure of [K(18-crown-6)][PtCl3(PhC≡CD)] · CH2Cl2

Gerisch, Michael; Heinemann, Frank W.; Bögel, Horst; Steinborn, Dirk

doi:10.1016/s0022-328x(97)00465-8

Cited by 21 publications

(17 citation statements)

References 30 publications

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“…0.1 Å longer for Ln(II) than Ln(III) . The crown ether-coordinated potassium in the cation of 6 shows K−O bond lengths similar to those found in related complexes, with K showing weak η 2 -interaction with two molecules of benzene located above and below the crown ether …”

supporting

confidence: 66%

The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η²-C₆H₆)₂][(LaCp^tt₂)₂(μ-η⁶:η⁶-C₆H₆)]•2C₆H₆ (Cp^tt = η⁵-C₅H₃Bu^t₂-1,3)

1998

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supporting

confidence: 66%

The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η²-C₆H₆)₂][(LaCp^tt₂)₂(μ-η⁶:η⁶-C₆H₆)]•2C₆H₆ (Cp^tt = η⁵-C₅H₃Bu^t₂-1,3)

1998

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“…Of the fragments employed here, well-defined vinylidene complexes are known for [Cr(CO) 5 ] ( Cr ) and [Mn(η 5 -C 5 H 5 )(CO) 2 ] ( Mn ), as well as complexes related to Rh and Ru-1-H , as discussed above. In contrast, Au-1 is known to support η 2 -alkynes (discussed above), and so is [PdCl 3 ] − ( Pd ) . The fragment [AuN((C 3 F 7 )C(Dipp)N 2 )], related to Au-3 , is also known to support alkyne ligands bound in an η 2 fashion; however, considering the number of times that η 2 -alkyne complexes have been proposed as intermediates in gold-catalyzed reactions, there is still a paucity of isolated examples of this type of compound. ,, The carbene fragment [AuIMes] + ( Au-2 ) has been included here as a further gold(I) complex representative of common catalyst precursors and is likely to favor the η 2 -alkyne tautomer.…”

Section: Resultsmentioning

confidence: 99%

Computational Discovery of Stable Transition-Metal Vinylidene Complexes

et al. 2014

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Experimental results have long suggested that catalyst optimization is an inherently multivariate process, requiring the screening of reaction conditions (temperature, pressure, solvents, precursors, etc.), catalyst structure (metal and ligands), and substrate scope. With a view to demonstrating the feasibility and utility of multivariate computational screening of organometallic catalysts, we have investigated the structural and electronic properties of a library of transition-metal-coordinated alkyne and vinylidene tautomers in different coordination environments. By varying the substituents on the organic moiety of 60 alkyne/vinylidene pairs we were able to capture and quantify the key structural and electronic effects on tautomer preference. For a carefully selected subset of substituents, the effects of metal and ancillary ligands were then explored. We have been able to formulate a protocol for assessing the stabilization of vinylidenes in transition-metal complexes, suggesting that the d 6 square-based-pyramidal metal fragment [RuCl 2 (PR 2 3 )(CCHR 1 )], combined with electron-withdrawing substituents R 1 and electron-rich groups R 2 , would provide the ideal conditions favoring the vinylidene form thermodynamically.

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“… Crystal structure of the anion [PtCl 3 (PhCCH)] − ( 2 ) together with a schematic representation; Φ =82.5°, ψ 1 =15.2(9)°, r CC =1.23(1) Å (as compared to 1.208(1) Å in free phenylacetylene) 20b…”

Section: Basic Concepts Of Carbophilic Activationmentioning

confidence: 99%

Catalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids

2007

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The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization. The quite remarkable correlation of their catalytic behavior with the available structural data, coordination chemistry, and organometallic reactivity patterns, including relativistic effects, allows the underlying principles of catalytic carbophilic activation by pi acids to be formulated. The spectrum of reactivity extends beyond their utility as catalytic and benign alternatives to conventional stoichiometric pi acids. The resulting reactivity profile allows this entire field of catalysis to be rationalized, and brings together the apparently disparate electrophilic metal carbene and nonclassical carbocation explanations. The advances in coupling, cycloisomerization, and structural reorganization--from the design of new transformations to the improvement to known reactions--are highlighted in this Review. The application of platinum- and gold-catalyzed transformations in natural product synthesis is also discussed.

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Synthesis and characterization of platinum(II) complexes with terminal alkynes analogous to Zeise's salt — structure of [K(18-crown-6)][PtCl3(PhC≡CD)] · CH2Cl2

Cited by 21 publications

References 30 publications

The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η²-C₆H₆)₂][(LaCp^tt₂)₂(μ-η⁶:η⁶-C₆H₆)]•2C₆H₆ (Cp^tt = η⁵-C₅H₃Bu^t₂-1,3)

The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η²-C₆H₆)₂][(LaCp^tt₂)₂(μ-η⁶:η⁶-C₆H₆)]•2C₆H₆ (Cp^tt = η⁵-C₅H₃Bu^t₂-1,3)

Computational Discovery of Stable Transition-Metal Vinylidene Complexes

Catalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids

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Synthesis and characterization of platinum(II) complexes with terminal alkynes analogous to Zeise's salt — structure of [K(18-crown-6)][PtCl3(PhC≡CD)] · CH2Cl2

Cited by 21 publications

References 30 publications

The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η2-C6H6)2][(LaCptt2)2(μ-η6:η6-C6H6)]•2C6H6 (Cptt = η5-C5H3But2-1,3)

The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η2-C6H6)2][(LaCptt2)2(μ-η6:η6-C6H6)]•2C6H6 (Cptt = η5-C5H3But2-1,3)

Computational Discovery of Stable Transition-Metal Vinylidene Complexes

Catalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids

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The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η²-C₆H₆)₂][(LaCp^tt₂)₂(μ-η⁶:η⁶-C₆H₆)]•2C₆H₆ (Cp^tt = η⁵-C₅H₃Bu^t₂-1,3)

The First Example of a Crystalline Subvalent Organolanthanum Complex: [K([18]crown-6)- (η²-C₆H₆)₂][(LaCp^tt₂)₂(μ-η⁶:η⁶-C₆H₆)]•2C₆H₆ (Cp^tt = η⁵-C₅H₃Bu^t₂-1,3)