An Intermediate in the Conversion of an Acetylene to a Vinyl Derivative: The Crystal and Molecular Structure of <i>trans</i>-Chloromethylbis(trimethylarsine)-platinum(II) Hexafluorobut-2-yne

Davies, Brian William; Puddephatt, Richard J.; Payne, Nicholas C.

doi:10.1139/v72-364

Cited by 38 publications

(16 citation statements)

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“…(1) and 2.402 (1) A) are in the expected range and are near to the Pt-As bond lengths observed in other complexes, for example /ra«s-PtCl2(As(CH3)3)2, Pt-As = 2.308 (2) A,17 Pt[o-phenylenebis(dimethylarsine)]22+, Pt-As = 2.375 (4) A,18 and Pt(F3CC2CF3)Cl(CH3> [As(CH3)3]2, Pt-As = 2.434 (4) A. 19 The significantly longer Pt-As bond trans to the carbon atom C(l) reflects the stronger trans influence of carbon compared with oxygen. 20 The platinum-carbon bond is 2.103 (7) A, slightly shorter than in complex II (2.138 (6) A) and the same as in the relatedo complex Pt[(NC)2C=C(CN)2]-[P(C6H6)3]215 (2.11 (3) A) or the Pt-sp2 C bond in the bis(acetylacetonato)chloroplatinate anion PtOC(CH3)-CHC(CH3)0[CH(COCH3)2]Cl of 2.106 (7) A.…”

mentioning

confidence: 89%

Structure and mechanism of formation of the metallooxacyclobutane complex bis(triphenylarsine)tetracyanooxiraneplatinum, the product of the reaction between tetracyanooxirane and tetrakis(triphenylarsine)platinum

Schlodder¹,

Ibers²,

Lenarda³

et al. 1974

J. Am. Chem. Soc.

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Metallooxacyclobutane complexes, Pt[C2(CN)40]L2 (L = P(C6H5)3, P(p-CH3C6H4)3, As(C6H5)3), were prepared from the reaction between tetracyanooxirane (2,2,3,3-tetracyanooxacyclopropane, C2(CN)40) and PtL4. The crystal and molecular structure of the complex where L = As(C6H5)3 has been determined from three-dimensional X-ray diffraction data. The crystal has symmetry consistent with the space group Ph/c [CV] with four molecules of the complex in a unit cell of dimensions a = 9.933 (2) A, b = 20.477 (3) A, c = 18.634 (3) A, and ß - 95.42 (1)°. The structure was refined by least-squares techniques to a conventional R index of 0.039 based on 4819 reflections above background collected using a four-circle diffractometer. The structure determination shows that Pt[As(C6H5)3]2 has inserted into the carbon-oxygen bond of the oxirane. Such a metallooxacyclobutane ring has recently been suggested as an intermediate in the catalytic formation of ethylene carbonate from Ni°c omplexes, ethylene oxide, and C02. Comparisons are made between the structural parameters of the present complex, the closely related metallocyclobutane complex Pt[C2(CN)4CH2][P(C6Hs)3]2, and the small rings tetracyanooxirane and 1,1,2,2-tetracyanocyclopropane. Spectroscopic data and chemical behavior of the metallooxacyclobutane complexes are reported.

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mentioning

confidence: 89%

Structure and mechanism of formation of the metallooxacyclobutane complex bis(triphenylarsine)tetracyanooxiraneplatinum, the product of the reaction between tetracyanooxirane and tetrakis(triphenylarsine)platinum

Schlodder¹,

Ibers²,

Lenarda³

et al. 1974

J. Am. Chem. Soc.

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“…6 The structure of the early alkyne and alkene complexes of Pt(II) was generally assigned on the basis of IR data, and only after quite a few years Puddephatt reported the first single crystal X-ray structure of a trigonal bipyramidal Pt(II) complex with an η 2 -coordinated alkyne, trans-[PtCl(Me)(η 2 -CF 3 CuCCF 3 )(AsMe 3 ) 2 ]. 7 Several penta-coordinate complexes, similar to those reported by Clark and Puddephatt, and having two halogens in apical positions and one chelate dinitrogen ligand and one ethylene in the trigonal plane, have been reported since 1973. 8 Their structures, initially assigned on the basis of NMR and IR data, were subsequently confirmed by single crystal X-ray diffraction analysis.…”

Section: Introductionmentioning

confidence: 54%

“…In this work we have investigated the reactivity of [PtX 2 (Me 2phen)] (X = Cl, 1; Br, 2; I, 3) complexes with acetylene. The chloro species, [PtCl 2 (Me 2 phen)], exhibits negligible reactivity while both the bromo, [PtBr 2 (Me 2 phen)], and iodo, [PtI 2 -(Me 2 phen)], species give formation of five-coordinate species of the type [PtX 2 (η 2 -CHuCH)(Me 2 phen)] (X = Br, I) which can Table 2 1 H and { 13 C} NMR data (δ, CDCl 3 ) for [PtX(η 1 -E-CHvCHX)(η 2 -CH 2 vCH 2 )(Me 2 phen)], X = Br, (7) and I, (12); syn and anti-[PtBr(η 1 -E-CHvCHBr)(η 2 -propene)(Me 2 phen)] (10); syn and anti-[PtBr(η 1 -E-CHvCHBr)(η 2 -cis-2-butene)(Me 2 phen)] ( 11); [PtBr(η 1 -E-CHvCHBr)(CuO)-(Me 2 phen)] ( 13); [PtI(η 1 -E-CHvCHI)(CuO)(Me 2 phen)] ( 14…”

Section: Discussionmentioning

confidence: 99%

Insertion of alkynes into Pt–X bonds of square planar [PtX₂(N^N)] (X = Cl, Br, I) complexes

et al. 2014

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The reactivity with acetylene of [PtX2(Me2phen)] (X = Cl, Br, I) complexes has been investigated. Whereas the chlorido species [PtCl2(Me2phen)] exhibits negligible reactivity at short reaction times, the bromido and iodido species [PtBr2(Me2phen)] and [PtI2(Me2phen)] lead initially to formation of Pt(II) five-coordinate complexes, [PtX2(η(2)-CH≡CH)(Me2phen)], that evolve to four-coordinate alkenyl complexes of the type [PtX(η(1)-E-CH=CHX)(Me2phen)]. The alkenyl complexes, in the presence of excess acetylene, establish an equilibrium with the five-coordinate alkyne-alkenyl species [PtX(η(1)-E-CH=CHX)(η(2)-CH≡CH)(Me2phen)] (X = Br, I). The π-bonded acetylene can be exchanged with free olefins or C≡O, affording the new alkene-alkenyl or carbonyl-alkenyl complexes [PtX(η(1)-E-CH=CHX)(η(2)-olefin)(Me2phen)] and [PtX(η(1)-E-CH=CHX)(C≡O)(Me2phen)]. The five-coordinate geometry of the alkyne-alkenyl and alkene-alkenyl complexes was assessed from NMR data and is fully consistent with that of a previously determined X-ray structure of [PtBr(η(1)-E-CH[double bond, length as m-dash]CHBr)(η(2)-CH2=CH2)(Me2phen)].

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“…Monosubstituted alkynes are also readily cyclotetramerized and both simple and functionalized tetramers may be synthesized. [151] With methyl propiolate, 66% of the monomer is converted in the presence of Ni(PCl 3 ) 4 catalyst at 33 • C, the yield of 1,2,4,6-tetramer is 83% and the remaining product (17%) is 1,2,4tricarbomethoxybenzene, as shown in eqn (15). [147,148,188] HC≡C-COOMe…”

Section: = S Sementioning

confidence: 99%

Three characteristic reactions of alkynes with metal compounds in organic synthesis

Omae

2008

Applied Organom Chemis

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IntroductionBoth alkynes and alkenes are compounds having at least one π -electron bond. Therefore, in these compounds, reactions such as the addition of hydrogen, the addition of halogens, the addition of hydrogen halides, metathesis, oxidation and polymerization, proceed in the presence of metal compounds.However, alkynes have another set of π -electron bonds. These two sets of π -electron bonds in alkynes are mutually orthogonal. Hence, the reactions of alkynes in the presence of the metal compounds are different from the reactions of alkenes.As described in the next section, the two sets of mutually orthogonal π -electron bonds tend to easily bond with d-electrons in transition metals. Consequently, the characteristic reactions of alkynes occur in the presence of the transition metals. In these transition metal compounds, especially, a Co-Co bond in (CO) 4 Co-Co(CO) 4 , very easily form a mutually bridged bond with the two sets of π -electron bonds in alkynes. These reactions of alkynes with alkenes in the presence of Co 2 (CO) 8 are the most characteristic reactions of alkynes with the transition metals in organic synthesis.This first type of characteristic reaction of alkynes with organocobalt compounds is the Pauson-Khand reactions. Reactions that are similar to the Pauson-Khand reactions, Pauson-Khand-type reactions, occur in the presence of the other transition metal compounds besides the cobalt carbonyl compounds, and also proceed as the first type of characteristic reactions. The Pauson-Khand reactions and Pauson-Khand-type reactions are the reactions of alkynes, alkenes and carbon monoxide. In these three components, alkynes and carbon monoxide have two sets of π -electron bonds and alkenes have one set of π -electron bond. These reactions are also called as the [2 + 2 + 1] cyclizations.The second type of characteristic reactions of alkynes with the transition metal compounds is other cyclizations in which alkynes react with compounds having π -electron bonds such as other alkynes, alkenes, allenes, aldehydes, ketones, imines, carbon monoxide, carbon dioxide and nitriles. These reactions are cyclooligomerizations and cycloadditions.The third type of characteristic reaction of alkynes in the presence of the metal compounds is coupling reactions in which the negative charge of the carbon atom in alkynes is involved in addition to the high reactivity to the π -electron bond. The reactions are carbonylations, dioxycarbonylations, coupling reactions with aldehydes, ketones, imines, alkenes, allyl compounds, alkynes, other oxygen-containing compounds or nitrogen-containing compounds, Sonogashira reactions and other coupling reactions.The characteristic reactions of alkynes with organocobalt compounds in organic synthesis have been reported in a previous review article. [1] This present review reports mainly on three characteristic reactions of alkynes with the metal compounds in organic synthesis, excluding the organocobalt compounds. * Correspondence to : Iwao Omae, Nihon Pharmaceutical University, 10281 ...

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An Intermediate in the Conversion of an Acetylene to a Vinyl Derivative: The Crystal and Molecular Structure of trans-Chloromethylbis(trimethylarsine)-platinum(II) Hexafluorobut-2-yne

Cited by 38 publications

References 19 publications

Structure and mechanism of formation of the metallooxacyclobutane complex bis(triphenylarsine)tetracyanooxiraneplatinum, the product of the reaction between tetracyanooxirane and tetrakis(triphenylarsine)platinum

Structure and mechanism of formation of the metallooxacyclobutane complex bis(triphenylarsine)tetracyanooxiraneplatinum, the product of the reaction between tetracyanooxirane and tetrakis(triphenylarsine)platinum

Insertion of alkynes into Pt–X bonds of square planar [PtX₂(N^N)] (X = Cl, Br, I) complexes

Three characteristic reactions of alkynes with metal compounds in organic synthesis

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An Intermediate in the Conversion of an Acetylene to a Vinyl Derivative: The Crystal and Molecular Structure of trans-Chloromethylbis(trimethylarsine)-platinum(II) Hexafluorobut-2-yne

Cited by 38 publications

References 19 publications

Structure and mechanism of formation of the metallooxacyclobutane complex bis(triphenylarsine)tetracyanooxiraneplatinum, the product of the reaction between tetracyanooxirane and tetrakis(triphenylarsine)platinum

Structure and mechanism of formation of the metallooxacyclobutane complex bis(triphenylarsine)tetracyanooxiraneplatinum, the product of the reaction between tetracyanooxirane and tetrakis(triphenylarsine)platinum

Insertion of alkynes into Pt–X bonds of square planar [PtX2(N^N)] (X = Cl, Br, I) complexes

Three characteristic reactions of alkynes with metal compounds in organic synthesis

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Insertion of alkynes into Pt–X bonds of square planar [PtX₂(N^N)] (X = Cl, Br, I) complexes