[Bis(phosphonio)isophosphindolide]silver Complexes

Gudat, Dietrich; Schrott, Martin; Bajorat, Volker; Nieger, Martin; Kotila, Sirpa; Fleischer, Roland

doi:10.1002/cber.19961290315

Cited by 29 publications

(26 citation statements)

References 22 publications

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“…4a) is similar as in phosphenium complexes [1 -3], but the P-Cu bonds (2.199(2) A) are slightly longer than in the phosphane complex [(Cy3P)2Cu2(^-C l)2] (2.18 A [17]) and fail thus to show the expected [3] bond shortening. Similar features had also been noted for gold and silver complexes of 1 [5,8 ]. Unlike the irregular T-shaped metal coordination geometry in 2 [8 ], all bond angles at C u(l) lie in a narrow range of 120 ± 3°.…”

Section: Crystal Structuressupporting

confidence: 53%

“…Similar features had also been noted for gold and silver complexes of 1 [5,8 ]. Unlike the irregular T-shaped metal coordination geometry in 2 [8 ], all bond angles at C u(l) lie in a narrow range of 120 ± 3°.…”

Section: Crystal Structuressupporting

confidence: 53%

“…Among the different types [3] of such cations, bis-phosphonio-isophosphindolides like 1 14] are unique because their low Lewis acidity allows the formation of stable complexes even with electrophilic metal centers such as univalent coinage metal cations [5 -8 ]. As is exemplified by the reactivity of 1 towards Ag+ (Scheme 1) [8 ], these complexes include both mononuclear com pounds (2) with / / 1 (P)-and dinuclear complexes (3) with //2(P)-coordination of the ligand. With respect to its coordination properties, the cation 1 behaves thus as a hybrid between a phosphenium ion which occurs exclusively as a 2 -electron donating ligand, and a (^V 'F^-c o o rd in a te d phospholide anion [9] which acts as a 4-electron donor.…”

Section: Introductionmentioning

confidence: 99%

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Bis-phosphonio-isophosphindolide Copper Complexes

Gudat

Holderberg

Korber

et al. 1999

Zeitschrift Für Naturforschung B

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Phosphorus Heterocycles, Copper Complexes, Crystal Structure, '' P NMR Data Bis-triphenylphosphonio-isophosphindolide salts 1[X] react with Cu(I)-halides CuX to give isolable products of composition [(l)Cu2X3]. X-ray crystal structure analyses confirmed that for X = Br, Cl dinuclear complexes [(/y-1 )(/i-X)Cu2X2] with /i2j;'(P)-bridging cations 1 are formed, while for X = I a solid phase containing a salt (l^lC u*^] and a complex [(l^C u .^] with a terminal ?/(P)-coordinated ligand 1 was obtained. The bonding parameters in the two types of complexes suggest that l i s a hybrid between a phosphenium cation and a phospholide anion whose 7T-system is less nucleophilic than the phosphorus lone-pair.31P NMR studies revealed that in solution in all cases binuclear complexes [(l)Cu2X3] are in dynamic equilibrium with small amounts of mononuclear species and free 1. The same equilibria were detected in the system l[OTf]/CuOTf. NMR studies of ligand exchange reactions indicated that the stability of complexes [(l)Cu2X3] increases in the order X = OTf < 1 < Br, Cl, and titration of [(l)Cu2Bn] with EuNBr allowed to determine the equilibrium constant of the complex formation reaction.

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Section: Crystal Structuressupporting

confidence: 53%

Section: Crystal Structuressupporting

confidence: 53%

Section: Introductionmentioning

confidence: 99%

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Bis-phosphonio-isophosphindolide Copper Complexes

Gudat

Holderberg

Korber

et al. 1999

Zeitschrift Für Naturforschung B

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“…All findings suggest that the bonding in the Ag 2 P unit of [AgA C H T U N G T R E N N U N G (dap)] should not be described as two electron-precise single bonds like in m 2 (P)-phospholyl complexes, but rather, as in the m 2 (P)-bis-phosphonio-benzophospholide complex, [13] in terms of an electron-deficient three-center bond that involves predominantly the phosphorus lone pair and hardly perturbs the p-electron system of the ligand.…”

Section: H T U N G T R E N N U N G (Dap) 2 ] and [Ag-mentioning

confidence: 92%

“…[7] The P À Ag bonds (2.551(1), 2.537(1) ) are longer than in tertiary phosphine complexes (Ag À P 2.44 AE 0.07 [12] ) or in a complex with a m 2 (P)-bound bis-phosphonio-benzophospholide donor (AgÀP 2.37-2.42 ) [13] but match the distances in disilver complexes with m 2 (P)-bridging phosphole units (AgÀP 2.48-2.86 [9] ). All findings suggest that the bonding in the Ag 2 P unit of [AgA C H T U N G T R E N N U N G (dap)] should not be described as two electron-precise single bonds like in m 2 (P)-phospholyl complexes, but rather, as in the m 2 (P)-bis-phosphonio-benzophospholide complex, [13] in terms of an electron-deficient three-center bond that involves predominantly the phosphorus lone pair and hardly perturbs the p-electron system of the ligand.…”

Section: H T U N G T R E N N U N G (Dap) 2 ] and [Ag-mentioning

confidence: 99%

Metal Dependence of Network Dimensionality in 1,2,4‐Diazaphospholide Coordination Polymers

Schramm

Leineweber²,

Lissner

et al. 2010

Chemistry A European J

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Coordination polymers constructed from metals and bridging organic ligands are currently being intensely explored because they offer interesting physical properties or potential uses (e.g. for ion exchange, adsorption, and catalysis).[1] Although various structural architectures are easily synthesized, [2] control in the assembly of the network topology is still a great challenge. Five-membered heteroaromatics with several Group 15 donor atoms have recently been employed with some success because they offer rigid structures that support directional metal coordination, and a tendency to form polynuclear clusters that can serve as defined building blocks. Examples with polydentate N-donor ligands include pyrazolide (pz) and 1,2,4-triazolide (trz) based coordination polymers with 1D to 3D network topologies, [3,4] and pentaphosphaferrocenes [(R 5 C 5 )Fe(P 5 )] have been employed as building blocks to construct P-donor-based 1D and 2D polymeric networks and spherical oligomeric assemblies (Scheme 1).[5]The successful utilization of both P-and N-based homotopic ligands suggested that heterotopic P,N-heterocycles are likewise viable building blocks, in which the presence of two types of donor sites with different ligating power might allow, as an additional advantage, the observation of switchable coordination behavior. In particular, we envisaged that the known preference of the two-coordinate phosphorus to behave as soft donor should allow the ligand to use both Pand N-donor functions to bind to soft metal ions, whereas only N-donor sites should be involved in binding of hard metal ions, thus enabling the construction of coordination polymers with different network topologies from the same ligand. Here, we report on the results of some initial experiments conducted along these lines. The bridging ligand employed, 1,2,4-diazaphospholide (dap), [6] was chosen because its hydrolytic stability offers the prospect of developing the coordination chemistry of low-coordinate phosphorus compounds in aqueous solution, and because 1,2,4-diazaphospholides form molecular complexes with a remarkable variability of bonding modes.[7] Although m-bridging coordination modes have been established in several of these complexes, it seems, however, that the deliberate synthesis of coordination polymers has not been attempted.Experiments aimed at the syntheses of 1,2,4-diazaphospholide salts with distinguishable network topologies were performed by reacting aqueous solutions of 1,2,4-diazaphosphole (dapH) with zinc chloride and silver nitrate, respectively. Zinc(II) is known to form a variety of stable complexes with N-donors but lacks a strong affinity for Pdonors, whereas silver(I) binds easily to both types of ligands and even has a slight preference for P-coordination. The products precipitated upon mixing of the reactants as colorless, microcrystalline solids that were insoluble in common organic solvents and were characterized by elemental analyses, solid-state 31 P and 13 C NMR spectroscopy, and powder X-ray diffraction studies. Th...

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Synthesis of Organouranium(IV) Triflates from U(OTf)4 or from Alkyl or Amide Precursors

Berthet

Nierlich

Ephritikhine

2002

Eur. J. Inorg. Chem.

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The uranium(IV) triflate [U(OTf)4] (1) (OTf = OSO2CF3) gives stable adducts with Lewis bases, such as [U(OTf)4(py)] (2) (py = pyridine). The crystal structure of a solvate of [U(OTf)4(OPPh3)3] (3), which exhibits a bidentate OTf group, has been determined. Substitution of the triflate ligands of 1 with LiNEt2, Kacac (acac = MeCOCHCOMe), KCp (Cp = η‐C5H5), and K2COT (COT = η‐C8H8) has led to the formation of [U(NEt2)4], [U(acac)4], [U(Cp)3(OTf)] (4), and [U(COT)(OTf)2(py)] (5), respectively. However, the bis(cyclopentadienyl) compounds [U(Cp*)2(OTf)2] (6) (Cp* = η‐C5Me5) and [U(Cp)2(OTf)2(py)] (7) could not be prepared from 1. Complexes 4−7 have been isolated in good yields from the protonolysis reactions of the corresponding alkyl or amide precursors by means of pyridinium triflate. Compound 5 has also been prepared by treating [U(COT)2] with either [pyH][OTf] or 1 in pyridine. The crystal structures of [U(Cp)2(OTf)2(py)2] (8) and [U(COT)(OTf)2(OPPh3)2]·0.5py (9) have been determined.

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[Bis(phosphonio)isophosphindolide]silver Complexes

Abstract: Key Words-Bis(phosphonio)isophosphindolide cations I Silver complexes I 31P NMR I "'Ag NMR 2 1 X C1(3a), Br (3b)

Cited by 29 publications

References 22 publications

Bis-phosphonio-isophosphindolide Copper Complexes

Bis-phosphonio-isophosphindolide Copper Complexes

Metal Dependence of Network Dimensionality in 1,2,4‐Diazaphospholide Coordination Polymers

Synthesis of Organouranium(IV) Triflates from U(OTf)4 or from Alkyl or Amide Precursors

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