[Bis(dicyclohexylphosphino)ethane]platinum(0). Reactions with alkyl, (trimethylsilyl)methyl, aryl, benzyl, and alkynyl carbon-hydrogen bonds

Hackett, Marifaith.; Whitesides, George M.

doi:10.1021/ja00213a016

Cited by 173 publications

(103 citation statements)

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“…The reductive elimination of neopentane from 141 [261] yields a highly reactive Pt 0 compound as an intermediate, which at 80 8C oxidatively adds dimethylimidazolium iodide to give the hydrido complex 142 (Scheme 73). [260] This method is only applicable for sterically less-demanding N,N'-substituted imidazolium salts [262] to electron-rich and coordinatively unsaturated complexes of the type [M 0 (NHC) 2 ] (M = Ni, Pd) which were generated in situ.…”

Section: Angewandte Chemiementioning

confidence: 99%

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

2008

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The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of beta-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

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Section: Angewandte Chemiementioning

confidence: 99%

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

2008

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“…[102] The characterization of the products was often achieved by in situ NMR spectroscopy of the reaction solution. [128,129] with R 3 E (R CH 2 tBu, CH 2 SiMe 3 ; E Al, Ga, In; L (C 6 H 11 )PCH 2 CH 2 P(C 6 H 11 )) as reaction partner and at the same time as solvent [Eq. (7)].…”

Section: Bimolecular Addition Reactions Of Alkyl Earth Metal Compoundmentioning

confidence: 99%

“…The reactive fragment thus formed, [cis-(L) 2 Pt], then is available for a series of subsequent reactions. [128,129] It has to be emphasized that the course of the reaction is strongly influenced by small variations of the groups R. According to Equation (8) quantitative alkylation or alkyl exchange and the formation of [(L) 2 PtR 2 ] is observed for R CH 3 , C 2 H 5 , isobutyl. The work of Schneider et al on the interaction of alkylaluminum compounds with transition metal fragments should be noted in this context.…”

Section: Bimolecular Addition Reactions Of Alkyl Earth Metal Compoundmentioning

confidence: 99%

Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

Fischer

Weiß

1999

Angew. Chem. Int. Ed.

208

101

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The current upswing in the interest in organoelement chemistry of Group 13 metals is attributed not least to the establishment of the coordination chemistry of R(a)E fragments (E=Al, Ga, In; a=1, 2) at d-block metals (M). Recently the availability of low-valent organoelement compounds as building blocks for synthesis has substantially enriched the structure chemistry of this class of compounds. The M-E bonding conditions and the question of the significance of M(d(pi))-E(p(pi)) backbonding as well as potential applications in materials science, for example, as single-source precursors for the deposition of thin intermetallic films by chemical vapor deposition, are discussed.

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“…The only precedent for such selectivity of mesitylene oxidative addition to a platinum atom is the d 10 transient [Pt(Cy 2 PC 2 H 4 PCy 2 )]. [13,14] At the same time, formation of mixtures of isomeric aryl-and benzylplatinum(ii) complexes as products of methylarene activation with platinum(ii) complexes is known. [15] Thus, the influence of X ¼ H versus X ¼ Me in transient [LPtX] þ is controlled by both the thermodynamics and kinetics of the reductive elimination of the resulting [LPtH(R)X] þ .…”

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confidence: 99%

Control of HC(sp ³ ) Bond Cleavage Stoichiometry: Clean Reversible Alkyl Ligand Exchange with Alkane in [LPt(Alk)(H) ₂ ] ⁺ (L=[2.1.1]‐(2,6)‐Pyridinophane)

Vedernikov

Caulton

2002

Angewandte Chemie Intl Edit

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The ability of platinum compounds to activate methane catalytically in aqueous solution was first described more than 30 years ago. [1] Determining the mechanism of the Shilov reaction, which was considered to be an oxidative addition of an alkane to a platinum(ii) center, remained challenging for over 25 years. First, increasingly persistent alkylhydridoplatinum(iv) complexes have been discovered, [2] and then the ability of platinum(ii) species to add hydrocarbons to produce very stable platinum(iv) alkyl hydrides was demonstrated. [3] Recent work [4] has shown that the transient [LPtCH 3 ] þ , where L is a ligand that cannot structurally accommodate the square-planar geometry preferred by four-coordinate Pt II species and only modestly stabilizes the related octahedral alkane oxidative addition products, cleaves alkane CÀH bonds. Here L is [2.1.1]-(2,6)-pyridinophane, and the transient is available according to Equation (1) in Scheme 1. This transient cleaves one substrate C À H bond, but methane is eliminated easily from the Pt IV intermediate 1; b-H elimination from the derived Pt II alkyl compound then leads to net conversion of alkane to (coordinated) olefin, thus accomplishing a second substrate CÀH bond cleavage.To obtain alkane activation products different from the hydrido olefin complexes, we suggest here a modification of the starting dialkylhydridoplatinum(iv) complex to allow only an alkane single CÀH bond activation event. For this we needed a species with a single alkyl ligand attached to a platinum(iv) center which will leave one hydride in the transient [LPtX] þ (X ¼ H) species. As a synthetic source of this transient, we initially considered whether [LPtMe(H) 2 ] þ would selectively eliminate methane rather than H 2 . The same question has been addressed recently for the complex TpPtMeH 2 . [5] The free energies for methane and for H 2 elimination from [LPtMe(H) 2 ] þ were calculated (DFT, PBE functional, [6] SBK basis set, [7] and program package Priroda [8] ; Figure 1) and show that methane elimination is favored, both thermodynamically and kinetically, [9] by more than 13 kcal mol À1 relative to H 2 elimination. Due to the macrocycle constraints, Pt II cannot achieve a planar four-coordinate geometry in [LPtH] þ (Figure 1), and the best geometry is three-coordinate T-shaped, with only 14 valence electrons. The out-of-plane pendant N3 atom interacts negligibly with the Pt II center, and the longer distance of Pt to N2 than to N1 shows the trans influence of hydride. [10] Based on the energies in Figure 1, we expected to develop reversible alkane single C À H bond activation chemistry with a [LPtH] þ transient; this is unprecedented for Pt II .The synthesis of [LPtMe(H) 2 ] þ , [11] as its [BAr F 4 ] À salt (Ar F ¼ 3,5-(CF 3 ) 2 C 6 H 3 ), is summarized in Equation (2) (> 98 % yield based on NMR data, relative to signal for BAr F 4 ; yield of isolated product 85 %). The new dihydridoplatinum(iv) complex is air-and water-stable and can be recrystallized from a warm water±methanol mixture. No...

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[Bis(dicyclohexylphosphino)ethane]platinum(0). Reactions with alkyl, (trimethylsilyl)methyl, aryl, benzyl, and alkynyl carbon-hydrogen bonds

Cited by 173 publications

References 0 publications

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

Control of HC(sp ³ ) Bond Cleavage Stoichiometry: Clean Reversible Alkyl Ligand Exchange with Alkane in [LPt(Alk)(H) ₂ ] ⁺ (L=[2.1.1]‐(2,6)‐Pyridinophane)

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[Bis(dicyclohexylphosphino)ethane]platinum(0). Reactions with alkyl, (trimethylsilyl)methyl, aryl, benzyl, and alkynyl carbon-hydrogen bonds

Cited by 173 publications

References 0 publications

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

Control of HC(sp 3 ) Bond Cleavage Stoichiometry: Clean Reversible Alkyl Ligand Exchange with Alkane in [LPt(Alk)(H) 2 ] + (L=[2.1.1]‐(2,6)‐Pyridinophane)

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Control of HC(sp ³ ) Bond Cleavage Stoichiometry: Clean Reversible Alkyl Ligand Exchange with Alkane in [LPt(Alk)(H) ₂ ] ⁺ (L=[2.1.1]‐(2,6)‐Pyridinophane)