Nickel(II), palladium(II), and platinum(II) complexes containing cis- or trans-1,2-bis(diphenylphosphino)ethene: isomorphous crystal structures in the cyanide case

Oberhauser, Werner; Bachmann, Christian; Stampfl, Thomas; Haid, Rainer; Langes, Christoph; Rieder, Alexander; Brüggeller, Peter

doi:10.1016/s0277-5387(98)00093-x

Cited by 22 publications

(24 citation statements)

References 9 publications

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“…[68] The Pt- . [69] The Pt-CH 3 [72] An almost identical distance [2.052(7) Å] was found for the Pt-Ph bond in the similar non-fluorinated compound [PtPh(κ 2 -2-C 6 H 4 PPh 2 )(PPh 3 )]. [73] The X-ray structure of trans-6 confirms the presence of monodentate trifluoroacetate, the Pt-O distance being 2.118(2) Å.…”

Section: Salts Cis-[ptlmentioning

confidence: 75%

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)

et al. 2008

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Treatment of the bis(chelate) complex cis-[Pt(κ 2 -C 6 H 3 -5-Me-2-PPh 2 ) 2 ] (1) with strong acids causes selective cleavage of one of the metal-aryl bonds to give cis-[PtX(κ 2 -C 6 H 3 -5-Me-2-PPh 2 )(PPh 2 -4-tol)] [X = Cl (2), Br (3), I (4), ONO 2 (5) and OCOCF 3 (6)], from which a series of neutral and cationic derivatives can be derived by metathetical reactions. The complexes 2 and 6 rearrange spontaneously to the corresponding trans isomers, this reaction being promoted by CO. The J(Pt-P) values for the phosphorus atom of the four-membered ring can be ordered to establish a trans-influence series of anionic ligands X and neutral ligands L, which correlates well with, but is more extensive than, that based earlier on PtMe(dppe) complexes. Single-crystal X-ray structural analysis of trans-[Pt(κ 1 -OCOCF 3 )(κ 2 -C 6 H 3 -5-Me-2-PPh 2 )(PPh 2 -4-tol)] (trans-

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Section: Salts Cis-[ptlmentioning

confidence: 75%

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)

et al. 2008

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“…The structures of 1 and 14 fulfill the criteria of the same ligands, the same coordination number and geometry, isomorphous crystal lattices and equal experimental conditions, and, therefore, allow an exact comparison of their geometric features 24. The quadrant effect in 14 , given by the deviations of the four ipso carbon atoms C(11), C(21), C(31) and C(41) of –1.169(5), 1.647(5), 0.217(6) and –2.080(5) Å, respectively, from the coordination plane defined as above, is nearly identical to 1 .…”

Section: Resultsmentioning

confidence: 99%

The Influence of Steric Pressure on the Structure of Homodimetallic Rhodium(I) and Iridium(I) Complexes Containing a Bis(bidentate) Phosphane Ligand

et al. 2007

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P{ 1 H}), mass spectrometry, IR spectroscopy, elemental analyses and melting points. Furthermore, the solid-state structures of seven of these new compounds were fully determined by single-crystal X-ray diffraction analyses to study the influence of steric pressure. The precursor complex [Rh 2 (η 4 -cod) 2 (dppcb)]X 2 (1), X -= BF 4 -, PF 6 -, SbF 6 -, completely characterized by its X-ray structure, smoothly reacts with mono-or bidentate ligands containing phosphorus or nitrogen donor atoms. Thus, monophosphanes and monophosphites produce compounds of the structure type [Rh 2 L 4 (dppcb)](SbF 6 ) 2 [L = PMe 2 Ph, 2; PMePh 2 , 3; P(OMe) 3 , 5; P(OPh) 3 , 6]. The X-ray structures of 3 and 6 show that PMePh 2 and P(OPh) 3 are capable of compensating steric interactions. The treatment of 1 with diphosphanes leads to the structure type [Rh 2 L 2 (dppcb)](SbF 6 ) 2 [L = bis(diphosphanyl)-methane, dppm, 7; bis(diphenylphosphanyl)amine, dppam, 8; 1,2-bis(diphenylphosphanyl)ethane, dppe, 9; cis-1,2-

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“…2b,5 Surprisingly, also the new heterodimetallic species [Ru(bpy) 2 (dppcb)MCl 2 ]X 2 (M = Pt, 2; Pd, 3; X = PF 6 , SbF 6 ) are photochemically reactive, where the "steric pressure" is clearly reduced due to the presence of sterically less demanding square-planar metal centres (see Scheme 1). 2b,5,7 However, in the case of [Ru(bpy) 2 (dppcb)NiCl 2 ]X 2 (4; X = PF 6 , SbF 6 ) the reduction of the square-planar stabilization energy of nickel(II) compared with platinum(II) and palladium(II) 8 makes 4 flexible enough to enhance the non-radiative decay of its excited states. 2b,5 As a consequence for 4 neither a long-lived excited state at ambient temperature can be observed nor a photochemical product can be isolated.…”

Section: Introductionmentioning

confidence: 99%

Surprising photochemical reactivity and visible light-driven energy transfer in heterodimetallic complexes

et al. 2011

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The bis(bidentate) phosphine cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane (dppcb) has been used for the synthesis of a series of novel heterodimetallic complexes starting from [Ru(bpy)(2)(dppcb)]X(2) (1; X = PF(6), SbF(6)), so-called dyads, showing surprising photochemical reactivity. They consist of [Ru(bpy)(2)](2+)"antenna" sites absorbing light combined with reactive square-planar metal centres. Thus, irradiating [Ru(bpy)(2)(dppcb)MCl(2)]X(2) (M = Pt, 2; Pd, 3; X = PF(6), SbF(6)) dissolved in CH(3)CN with visible light, produces the unique heterodimetallic compounds [Ru(bpy)(CH(3)CN)(2)(dppcb)MCl(2)]X(2) (M = Pt, 7; Pd, 8; X = PF(6), SbF(6)). In an analogous reaction the separable diastereoisomers (ΔΛ/ΛΔ)- and (ΔΔ/ΛΛ)-[Ru(bpy)(2)(dppcb)Os(bpy)(2)](PF(6))(4) (5/6) lead to [Ru(bpy)(CH(3)CN)(2)(dppcb)Os(bpy)(2)](PF(6))(4) (9), where only the RuP(2)N(4) moiety of 5/6 is photochemically reactive. By contrast, in the case of [Ru(bpy)(2)(dppcb)NiCl(2)]X(2) (4; X = PF(6), SbF(6)) no clean photoreaction is observed. Interestingly, this difference in photochemical behaviour is completely in line with the related photophysical parameters, where 2, 3, and 5/6, but not 4, show long-lived excited states at ambient temperature necessary for this type of photoreaction. Furthermore, the photochemical as well as the photophysical properties of 2-4 are also in accordance with their single crystal X-ray structures presented in this work. It seems likely that differences in "steric pressure" play a major role for these properties. The unique complexes 7-9 are also fully characterized by single-crystal X-ray structure analyses, clearly showing that the stretching vibration modes of the ligand CH(3)CN, present only in 7-9, cannot be directly influenced by "steric pressure". This has dramatic consequences for their photophysical parameters. The trans-[Ru(bpy)(CH(3)CN)(2)](2+) chromophore of 9 acts as efficient "antenna" for visible light-driven energy transfer to the Os-centred "trap" site, resulting in k(en) ≥ 2 × 10(9) s(-1) for the energy transfer. Since electron transfer is made possible by the use of this intervening energy transfer, in dyads like 2-4 highly reactive M(0) species (M = Pt, Pd, Ni) could be generated. These species are not stable in water and M(II) hydride intermediates are usually formed, further reacting with H(+) to give H(2). Thus, derivatives of 3, namely [M(bpy)(2)(dppcb)Pd(bpy)](PF(6))(4) (M = Os, Ru) dissolved in 1:1 (v/v) H(2)O-CH(3)CN produce H(2) during photolysis with visible light.

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Nickel(II), palladium(II), and platinum(II) complexes containing cis- or trans-1,2-bis(diphenylphosphino)ethene: isomorphous crystal structures in the cyanide case

Cited by 22 publications

References 9 publications

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)

The Influence of Steric Pressure on the Structure of Homodimetallic Rhodium(I) and Iridium(I) Complexes Containing a Bis(bidentate) Phosphane Ligand

Surprising photochemical reactivity and visible light-driven energy transfer in heterodimetallic complexes

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Nickel(II), palladium(II), and platinum(II) complexes containing cis- or trans-1,2-bis(diphenylphosphino)ethene: isomorphous crystal structures in the cyanide case

Cited by 22 publications

References 9 publications

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A 31P NMR trans‐Influence Series Based on the Unit Pt(κ2‐C6H3‐5‐Me‐2‐PPh2)(PPh2‐4‐tol)

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A 31P NMR trans‐Influence Series Based on the Unit Pt(κ2‐C6H3‐5‐Me‐2‐PPh2)(PPh2‐4‐tol)

The Influence of Steric Pressure on the Structure of Homodimetallic Rhodium(I) and Iridium(I) Complexes Containing a Bis(bidentate) Phosphane Ligand

Surprising photochemical reactivity and visible light-driven energy transfer in heterodimetallic complexes

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Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)