Darstellung und spektroskopische Eigenschaften von planaren Dipseudohalogeno-bis(phosphin)-platin(II)-Komplexen / Preparation and Spectroscopic Properties of Planar Dipseudohalogeno-bis(phosphine)-platinum(II) Complexes

Kreutzer, P.; Schorpp, Karl; Beck, Wolfgang

doi:10.1515/znb-1975-7-815

Cited by 28 publications

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“…The comparatively low solubility of cis-[PtC12-( P B u~~)~] also prevented us from measuring concentration dependence in a range of solvents but in CH2C12 the variation was the inverse of that observed for the trans isomer, being approximately linear from 3510.1 Hz at 50 mg ml-I to 3501.0 Hz at 825 mg ml-l. The recent report (5) of solvent dependence of lJPtVP in cis-[PtC12-( P B u~~)~] does not specify the concentrations used. The data include only three solvents (CH2C12, CHCl3, and (CH3)2C0, lJptPp = 3505, 3508, and 3487 respectively) in common with our study and in each case the coupling constants are slightly lower than those given in Table 1.…”

Section: Coupling Cons Tan Tsmentioning

confidence: 99%

“…Very few examples of solvent dependent couplings involving 31P have been studied; the only examples being lJpH in pH3, PH(OCH3)2, and PH(CF3)2, 'JpF in the last compound (12)(13)(14), and the limited lJpt+ data mentioned above (5). We therefore considered it of interest to examine the effect of the usual laboratory variables in the nmr experiment (i.e.…”

Section: Introductionmentioning

confidence: 99%

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Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl₂(PBu₃ⁿ)₂]

Dixon¹,

Fakley²,

Pidcock³

1976

Can. J. Chem.

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. Can. J. Chem. 54, 2733Chem. 54, (1976. Studies of the effects of solvent, concentration and temperature on the 31P nmr parameters of cis-and trans-[PtC12(PBun3)2] are reported. The coupling constants, lJFt-,, are markedly dependent upon all three variables but, in contrast to previous studies on non-coordination compounds, very little corresponding variation in chemical shifts is found. Results are discussed in terms of a solvent cavity model using reaction field, Stark and Macrae effects but it is concluded that a more specific model involving competitive solvation at platinum gives a better interpretation of the data. KEITH R. DIXON, MARTIN FAKLEY et ALAN PIDCOCK. Can. J. Chem. 54, 2733 (1976). Une Ctude sur les effets du solvant, de la concentration et de la temperature sur les parametres du rmn 31P du [PtC12(PBun3)2] cis et trans est rappcrtee. Les constantes de couplage 'JPt-, dependent d'une f a~o n marquee des trois variables mais contrairernent B des Ctudes prkddentes sur des composCs de non-coordination, on ne trouve qu'une trks petite correspondance dans la variation des dCplacements chimiques. Les rCsultats sont discutks en terme d'un modele de cage de solvant utilisant les effets de champs de rhction et les effets de Stark et ~Macrae toutefois, on en conclue qu'un modele plus spkifique impliquant une solvatation competitive du platine donne une meilleure interprktation des resultats.[Traduit par le journal]

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Section: Coupling Cons Tan Tsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl₂(PBu₃ⁿ)₂]

Dixon¹,

Fakley²,

Pidcock³

1976

Can. J. Chem.

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“…1, 2010 127 structure enantiomorph led to R 2 =0.044 and R 2w =0.063, full refinement of the wrong one led to R 2 =0.096 and R 2w =0.153. In the final Fourier maps, the maximum residuals were 1.94(13) e 3 A ˚-3 at 0.73 A ˚from Pt, 3.01(26) e 3 A ˚-3 at 0.83 A ˚from Pt, 1.71(18) e 3 A ˚-3 at 0.63 A ˚from Pt, 1.18(20) e 3 A ˚-3 at 0.08 A ˚from Cl2, 1.44(44) e 3 A ˚-3 at 1.03 A ˚from P1, 2.63(78) e 3 A ˚-3 at 0.62 A from Pt, 2.42(73) e 3 A ˚-3 at 0.55 A ˚from Pt, and 2.41…”

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confidence: 95%

Cooperation between Cis and Trans Influences in cis-Pt^II(PPh₃)₂ Complexes: Structural, Spectroscopic, and Computational Studies

et al. 2009

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The relevance of cis and trans influences of some anionic ligands X and Y in cis-[PtX(2)(PPh(3))(2)] and cis-[PtXY(PPh(3))(2)] complexes have been studied by the X-ray crystal structures of several derivatives (X(2) = (AcO)(2) (3), (NO(3))(2) (5), Br(2) (7), I(2) (11); and XY = Cl(AcO) (2), Cl(NO(3)) (4), and Cl(NO(2)) (13)), density functional theory (DFT) calculations, and one bond Pt-P coupling constants, (1)J(PtP). The latter have allowed an evaluation of the relative magnitude of both influences. It is concluded that such influences act in a cooperative way and that the cis influence is not irrelevant when rationalizing the (1)J(PtP) values, as well as the experimental Pt-P bond distances. On the contrary, in the optimized geometries, evaluated through B3LYP/def2-SVP calculations, the cis influence was not observed, except for compounds ClPh (21), Ph(2) (22), and, to a lesser extent, Cl(NO(2)) (13) and (NO(2))(2) (14). A natural bond order analysis on the optimized structures, however, has shown how the cis influence can be related to the s-character of the Pt hybrid orbital involved in the Pt-P bonds and the net atomic charge on Pt. We have also found that in the X-ray structures of cis-[PtX(2)(PPh(3))(2)] complexes the two Pt-X and the two Pt-P bond lengths are different each other and are related to the conformation of the phosphine groups, rather than to the crystal packing, since this feature is observed also in the optimized geometries.

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“…[26,29,173,192] The corresponding platinum complexes Pt(N 3 ) 2 (PR 3 ) 2 , on the other hand, are usually cis, both in the solid and in solution. [193] In higher nuclearity compounds and especially in coordination polymers, however, where metal bridging comes into play, azide (N 3 -) turns out to be a true champion in generating manifold modes of ligation (for details see Part I, chapter 3). [26] This applies to an even greater extent to tetrazoles and tetrazolate anions, which also give rise to various linkage isomers.…”

Section: Tetrazolato Metal Complexes: Coordination Modes Isomerism mentioning

confidence: 99%

Azide Chemistry – An Inorganic Perspective, Part II^[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

Fehlhammer

Beck

2015

Zeitschrift anorg allge chemie

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Abstract. In whatever state of bonding -whether covalent to an organic residue or a heteroatom, or polar to ionic in contact with a metal -the azide moiety N 3 is characterized by its high potential of reactivity which essentially manifests itself in two basic processes: the elimination of dinitrogen and the entry into 1,3-dipolar cycloadditions with suitable dipolarophiles, the latter of which clearly predominates the chemistry of azide, also that of its metal compounds. In a preceding review entitled "Part I -Metal Azides: Overview, General Trends and Recent Developments" which was meant to lay the foundations for the present paper, these and other reactions have already been touched upon. The present review -Part II -now focusses in great detail on the formation of five-membered heterocyclestetrazol(at)es, triazol(at)es, triazolin(at)es, thiatriazol(at)es, etc. as well as various consecutive products -from azide and nitriles, isocyanides, alkynes, alkenes and heteroallenes (CS 2 , RN=C=S) in the ligand sphere of the metal. Generally, these [3+2]-cycloadditions are found to CONTENTS

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Darstellung und spektroskopische Eigenschaften von planaren Dipseudohalogeno-bis(phosphin)-platin(II)-Komplexen / Preparation and Spectroscopic Properties of Planar Dipseudohalogeno-bis(phosphine)-platinum(II) Complexes

Cited by 28 publications

References 0 publications

Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl₂(PBu₃ⁿ)₂]

Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl₂(PBu₃ⁿ)₂]

Cooperation between Cis and Trans Influences in cis-Pt^II(PPh₃)₂ Complexes: Structural, Spectroscopic, and Computational Studies

Azide Chemistry – An Inorganic Perspective, Part II^[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

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Darstellung und spektroskopische Eigenschaften von planaren Dipseudohalogeno-bis(phosphin)-platin(II)-Komplexen / Preparation and Spectroscopic Properties of Planar Dipseudohalogeno-bis(phosphine)-platinum(II) Complexes

Cited by 28 publications

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Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl2(PBu3n)2]

Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl2(PBu3n)2]

Cooperation between Cis and Trans Influences in cis-PtII(PPh3)2 Complexes: Structural, Spectroscopic, and Computational Studies

Azide Chemistry – An Inorganic Perspective, Part II[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

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Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl₂(PBu₃ⁿ)₂]

Solvent, concentration, and temperature dependance of the platinum–phosphorus nuclear magnetic résonance coupling constants in cis- and trans-[PtCl₂(PBu₃ⁿ)₂]

Cooperation between Cis and Trans Influences in cis-Pt^II(PPh₃)₂ Complexes: Structural, Spectroscopic, and Computational Studies

Azide Chemistry – An Inorganic Perspective, Part II^[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems