Comparison of .sigma.-alkyl and .sigma.-perfluoroalkyl groups as ligands. 2. Crystal and molecular structures of dimethyl[(2-vinylphenyl)diphenylphosphine]platinum(II) and bis(trifluoromethyl)[(2-vinylphenyl)diphenylphosphine]platinum(II)

Bennett, Martin A.; Chee, Ho-Kin; Jeffery, John C.; Robertson, G. B.

doi:10.1021/ic50194a037

Cited by 39 publications

(20 citation statements)

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“…The bond lengths of Pt1–C1 and Pt1–C5 in Pt( n -C 4 F 9 ) 2 (cod) (2.060(8), 2.060(8) Å) are shorter than those in Pt( n -C 4 F 9 ) 2 (dppp) (2.109(4), 2.104(4) Å) owing to the larger trans effect of the phosphine ligand in comparison to that of the π-accepting olefin ligand. Pt(CF 3 ) 2 (L) (L = C 6 H 4 -1,2-(PPh 2 (CHCH 2 ))) was reported to contain Pt–CF 3 bonds with different lengths, depending on the ligand trans to the CF 3 group (2.082(6) Å (trans to P) and 2.032 Å (trans to vinyl)) …”

Section: Results and Discussionmentioning

confidence: 99%

“…A similar reaction yields the methyl(fluoroalkyl)platinum(II) complexes PtMeR F (L) (L = cod, nbd (norbornadiene), tmeda ( N , N , N ′, N ′-tetramethylethylenediamine); R F = CF 3 , n -C 3 F 7 , i -C 3 F 7 , n -C 4 F 9 ) and/or bis(fluoroalkyl)platinum complexes . The complexes have been employed as precursors of new fluoroalkyl platinum complexes having various auxiliary ligands . Vicic reported that the reaction of I–C 3 F 6 –I with PtMe 2 (cod) at room temperature affords Pt(C 3 F 6 I)Me(cod) as the initial product, and further reaction for 36 h at 90 °C converts it into a platinacyclobutane, Pt(C 3 F 6 )(cod), via oxidative addition of the remaining C–I bond to the Pt(II) center and by the elimination of MeI (Scheme B) .…”

Section: Introductionmentioning

confidence: 99%

“…8 The complexes have been employed as precursors of new fluoroalkyl platinum complexes having various auxiliary ligands. 9 Vicic reported that the reaction of I−C 3 F 6 −I with PtMe 2 (cod) at room temperature affords Pt(C 3 F 6 I)Me(cod) as the initial product, and further reaction for 36 h at 90 °C converts it into a platinacyclobutane, Pt(C 3 F 6 )(cod), via oxidative addition of the remaining C−I bond to the Pt(II) center and by the elimination of MeI (Scheme 1B). 8f Thus, the stepwise substitution of Me ligands by the fluorinated alkyl group takes place in these reactions, and the second step is slower than the first step.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Here, we report that the reaction of n-C 4 F 9 I with PtMe 2 (cod) is much smoother upon photoirradiation in 6) Å (trans to P) and 2.032 Å (trans to vinyl)). 9 The reaction was monitored by 1 H and 19 F{ 1 H} NMR spectroscopy. Figure 2A shows the change in the concentrations of the compounds in the reaction mixture, under UVirradiated conditions, which was monitored by the 1 H NMR spectra.…”

Section: ■ Introductionmentioning

confidence: 99%

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Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

2017

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The UV irradiation of a mixture of PtMe 2 (cod) (cod = 1,5cyclooctadiene) and n-C 4 F 9 I in a 1:12 molar ratio for 15 min produces Pt(n-C 4 F 9 ) 2 (cod) in 61% yield at room temperature. The reaction without irradiation, as reported previously, proceeds much more slowly; heating the mixture for 7 days at 50 °C forms PtMe(n-C 4 F 9 )(cod) in 9% yield and no Pt(n-C 4 F 9 ) 2 (cod). Pt(n-C 4 F 9 ) 2 (cod) is converted to complexes having chelating ligands, Pt(n-C 4 F 9 ) 2 (L) (L = dppe (1,2-bis(diphenylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), bpy (2,2′-bipyridine)). The photoassisted fluoroalkylation of PtMe(n-C 4 F 9 )(cod) also affords Pt(n-C 4 F 9 ) 2 (cod), while the monomethylplatinum complexes PtMe(C 6 H 4 -4-F)(cod) and PtClMe(cod) react with n-C 4 F 9 I under photoirradiation to afford complexes with a perfluorobutyl ligand, Pt(n-C 4 F 9 )(C 6 H 4 -4-F)(cod) and PtCl(n-C 4 F 9 )(cod), respectively. The above reactions do not provide isolable Pt(IV) complexes, in contrast to the reactions of alkyl or fluoroalkyl iodides with diorganoplatinum(II) complexes having dinitrogen ligands. The mechanism of the fluoroalkylation of Pt(II) complexes under photoirradiation is discussed on the basis of the reaction products.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

2017

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“…The C(1)-Pt-C(2) angle of 37.0-(5)°is approximately the same as the values observed in other known alkeneplatinum(II) complexes. 21,22 There exist intermolecular hydrogen bondings between the oxygen of the coordinated carboxylate group and the amine group of its neighboring molecule (O(1)‚‚‚N(1)′, 2.920 Å) and between the dangling carboxylate group and the amine group of its neighboring molecule (O(4)‚‚‚N(2)′, 2.803 Å). These intermolecular hydrogen bonds may give rise to additional stability for (O,alkene)chelation in the solid state.…”

Section: Resultsmentioning

confidence: 99%

Linkage Isomerism Dependent on Solvent and Temperature. Synthesis and Structural Properties of Diamineplatinum(II) Complexes of Allyl- and Diallylmalonate Ligands

1999

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The linkage isomerism between (O,O')- and (O,alkene)-chelates has been investigated for the complexes A(2)PtL(2) (A(2) = 2,2-dimethyl-1,3-propanediamine (DMPDA), trans-(+/-)-1,2-diaminocyclohexane (DACH); L(2) = allylmalonate (AM), diallylmalonate (DAM)). The crystal structures of (DMPDA)Pt(AM).2H(2)O (tetragonal P4(2)/m, a = 13.614(3) Å, b = 13.614(3) Å, c = 8.451(4) Å, V = 1566.3(9) Å(3), Z = 4, R = 0.0472) and (DMPDA)Pt(DAM).2H(2)O (monoclinic P2(1)/n, a = 11.021(3) Å, b = 8.996(2) Å, c = 18.765(7) Å, beta = 106.92(3) degrees, V = 1780.0(9) Å(3), Z = 4, R = 0.0531) have been solved. Each platinum atom adopts a typical square planar arrangement with two nitrogen atoms in cis positions. However, surprisingly, the AM anionic ligand is coordinated to the platinum atom via (O,O')-chelation mode through its two carboxylate groups with the alkene group uncoordinated in the solid state, breaking the hard/soft rule. The tetradentate DAM ligand is chelated to the platinum atom through one carboxylate and one alkene group resulting in (O,alkene)-chelation mode with another uncoordinated carboxylate and alkene group. Multinuclear ((1)H, (13)C, and (195)Pt) NMR studies clearly disclose that the linkage isomerism depends on the solvents employed. Both allyl- and diallylmalonate ligands are chelated exclusively to the platinum(II) atom via (O,O')-mode in dimethylformamide or Me(2)SO solution whereas only (O,alkene)-chelation mode is observed in an aqueous solution. At room temperature, the complexes both of the AM and DAM ligands exist in methanol as a mixture of (O,O')- and (O,alkene)-modes. Furthermore, interconversion between the two isomers occurs reversibly depending on temperature: the (O,alkene)-chelate is predominant at low temperatures while the (O,O')-chelate is favorable at elevated temperatures.

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Oxidative Addition of Halogens to Homoleptic Perfluoromethyl or Perfluorophenyl Derivatives of Platinum(II): A Comparative Study

Menjón¹,

Martínez-Salvador²,

Gómez‐Saso³

et al. 2009

Chemistry A European J

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Chlorocarbon solvents (solv=CH(2)Cl(2), CHCl(3)) are suggested to play an active role in the oxidative addition of halogens, X(2) (X=Cl, Br, I), to homoleptic d(8) perfluoromethyl and -phenyl platinum(II) species [Pt(R(F))(4)](2-) (R(F)=CF(3), C(6)F(5)). The perfluoromethyl group, CF(3), has been found to be considerably less prone to undergo reductive elimination processes, and is, therefore, more suitable for stabilizing organoplatinum(IV) derivatives (see scheme).The equilibrium geometries of the homoleptic perfluorinated organoplatinate(II) anions [Pt(CF(3))(4)](2-) and [Pt(C(6)F(5))(4)](2-) have been computed at the B3P86/LANL2DZ level of theory. Remarkably good agreement with the experimentally determined structures has been obtained by X-ray diffraction methods. The reactivity of [NBu(4)](2)[Pt(CF(3))(4)] (1) towards halogens (Cl(2), Br(2), and I(2)) has been investigated by using a combined experimental and theoretical approach. The perfluoromethyl derivative 1 has been found to undergo clean oxidative addition of the three halogens under investigation, giving rise to [NBu(4)](2)[trans-Pt(CF(3))(4)X(2)] (X=Cl (7), Br (10), I (13)) in a quantitative and stereoselective way. In the low-temperature reaction of the perfluorophenyl derivative [NBu(4)](2)[Pt(C(6)F(5))(4)] (3) with Cl(2) or Br(2), the corresponding oxidative-addition products [NBu(4)](2)[trans-Pt(C(6)F(5))(4)X(2)] (X=Cl (14), Br (15)) can also be obtained. In the case in which X=Br and working in CHCl(3) at -55 degrees C, it has been possible to detect the formation of an intermediate species to which we assign the formula [trans-Pt(C(6)F(5))(4)Br(ClCHCl(2))](-) (16). The solvento complex 16 is thermally unstable and prone to undergo reductive elimination of C(6)F(5)--C(6)F(5). In the presence of PhCN, complex [NBu(4)][trans-Pt(C(6)F(5))(4)Br(NCPh)] (17) was isolated and structurally characterized. The reaction of 3 with I(2) gave no organoplatinum(IV) compound. Our comparative study reveals that the CF(3) group is especially suited to stabilize organometallic compounds in high oxidation states. This ability can be attributed to a combination of factors: its hardness, its high group electronegativity, its small size, and its reluctance to undergo reductive elimination processes.

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Comparison of .sigma.-alkyl and .sigma.-perfluoroalkyl groups as ligands. 2. Crystal and molecular structures of dimethyl[(2-vinylphenyl)diphenylphosphine]platinum(II) and bis(trifluoromethyl)[(2-vinylphenyl)diphenylphosphine]platinum(II)

Cited by 39 publications

References 11 publications

Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

Linkage Isomerism Dependent on Solvent and Temperature. Synthesis and Structural Properties of Diamineplatinum(II) Complexes of Allyl- and Diallylmalonate Ligands

Oxidative Addition of Halogens to Homoleptic Perfluoromethyl or Perfluorophenyl Derivatives of Platinum(II): A Comparative Study

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